Color changing device for monitoring shelf-life of perishable products

ABSTRACT

A color changing device for monitoring the time-temperature storage history, i.e. shelf life, of perishable products. The device is constructed of an activator tape, containing an activator composition matrix, an indicating tape, containing an indicating composition matrix and an optional barrier matrix between the activator tape and the indicating tape. At least one matrix is a pressure sensitive adhesive. The activating composition, e.g. an organic acid such as citric acid, diffuses through the barrier and/or indicating matrix to continuously contact the indicating composition, e.g. an acid-base dye indicator such as 2,2&#39;,4,4&#39;,4&#34;,-pentamethoxy triphenylmethanol, to produce a visually observable color change at the temperature being monitored. The color intensifies with time and temperature, as more activator composition diffuses into the indicating matrix. The matrices are water-impermeable and the device preferably possesses activation energy and rate constant values for the color change which are substantially the same as those for product decay. This allows accurate and continuously observable monitoring of the abailable shelf-life of the perishable product to which the device is adhered to.

This invention was supported in part by a grant (#86-SBIR-8-0109) fromthe U.S. Department of Agriculture, under the Small Business InnovationResearch (SBIR) Program.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a color changing time-temperature historydevice for measuring the shelf-life of perishable products. The deviceis constructed of an activating tape, containing an activatorcomposition in a matrix and an indicating tape, containing an indicatingcomposition in a matrix. At least one of the matrices, is being apressure sensitive adhesive. The device may optionally contain abarrier, preferably a pressure sensitive adhesive, between theactivating tape and the indicating tape.

2. Brief Description of the Prior Art

Perishable products have measurable shelf-lives, which are usuallyexpressed within specified limits as the time left for available enduse. By the term "perishable products" is meant to include perishablefoods having a measurable shelf life such as fresh, refrigerated, andfrozen, vegetables, fruits, meats, fish, poultry, dairy products, bakeryproducts, juices, pre-cooked foods, soft and alcoholic beverages, andalso including nonfood items having extended shelf lives ranging from afew hours to some years including pharmaceuticals, vaccines, sera,blood, blood plasma, cosmetics, reactive chemical compounds, biochemicalproducts, batteries, x-ray film and photographic films. For example,FIG. 2 shows the shelf lives of various perishable products plotted innatural logarithm of shelf life in months against reciprocal of absolutetemperature resulting in straight line graphs. For example from thegraph, it can be seen that Eact's for corn cereal and strawberry are13.5 and 44.0 kcal/mole. The shelf lives for frozen asparagus, poultryand strawberry at 180° C. are 180, 360 and 630 days respectively.

A quantitative view of hypothetical product decay rates is seen inFIG. 1. In general, by plotting the natural logarithm of the shelf lifeor decay rate of product versus the reciprocal of the absolutetemperature (1/T in degrees Kelvin) a straight line is generallyobtained defining the temperature sensitivity characteristics of productdecay. The slope of the line is referred to as Eact.,(or E) the energyof activation of the product decay and the ordinate intercept (Yintercept) is a constant for the decay process. The same straight linegraph can be used to illustrate the rate characteristics for the colorchange of a device.

The well-known Arrhenius equation describes the characteristics of theabove-described straight line produced in FIG. 1:

    ln k=A-Eact/RT

where,

ln k=natural logarithm of the reaction rate

A=pre-exponent constant, also referred to as the rate constant

Eact=activation energy

R=universal gas constant

A=absolute temperature in degrees Kelvin.

FIG. 1 also illustrates difficulties involved in the use of atime-temperature history indicator device which undergoes an observablecolor change to monitor the shelf life of the perishable product atdifferent temperatures. If the perishable product decay is line B andthe indicator device is line A, then at Ti, it is seen that the productdecay and rate of color change of the indicator are identical and thusthe indicator will accurately monitor the shelf life of the perishableproduct at this temperature.

However, a problem arises if the perishable is stored at the highertemperature Th. In this case, the indicator A will undergo color changeprior to expiration of the usable shelf life of the product thus causingthe product to be prematurely discarded. Conversely, if the perishableis stored at lower temperature Tl, the shelf life of the product willexpire prior to the termination of the color change of the indicator, apotentially dangerous situation for those perishables which for example,can become contaminated with harmful bacteria, e.g. botulism. As is seenin FIG. 1, the problem with using the indicator A, to monitor the shelflife of perishable B, is that the slopes of the lines. i.e. energies ofactivation, are not identical in the temperature region of measurement.

Further, assuming that line C is the indicator and line B theperishable, it is seen that the two lines are parallel and haveidentical Eact's. However, since the rate constant (Y intercept) for Cis much lower than that for B, monitoring the shelf of the perishable Bat any temperature, will result in the indicator changing color at asignificantly earlier time prior to the end of the shelf life, resultingin a premature rejection of the product. The problem here is that eventhough the Eact for product decay and indicator color change areidentical, the rate constants for the two processes are different andthus lead to erroneous shelf life monitoring.

Thus, in order to be an effective indicator for monitoring the shelflife of perishable product, the characteristics of the indicator versusthe product must be such that preferably both the Eact and rate constantof the color change are substantially identical to those of productdecay of the perishable product, i.e. they both exhibit substantiallyidentical Arrhenius graphs in the temperature region of measurement.

Further, it is highly desirable as in the case of perishables having arelatively short shelf-life, i.e. milk, fish, eggs, and ice cream, to becontinuously aware of the remaining shelf-life of a perishable productso that contingencies can be made for their disposal, rather than beconfronted with an unexpected abrupt color change signifyingtermination. It is also desired that the device be in a form which iseasily manufactured and readily applied and adhered to the perishable,such as a "tape" device. Thus, what is highly desired in the art is amonitoring device preferably affixed to a perishable as a "tape", whichaccurately illustrates the remaining shelf life of the perishable.

A large number of devices have been reported in the patent literaturefor monitoring thermal degradation of perishables.

For example, several patents describe time-temperature monitoring (TTM)devices based on diffusion of liquids, vapors or gases through a barrierfilm. For example, in U.S. Pat. Nos. 4,195,056 and 4,195,058, G. N.Patel describes a device based on diffusion of vapor through a barrierfilm to introduce color change in the indicator on the other side of thebarrier. In order to prevent escape of the vapor, the device is sealedin a plastic container and requires a solvent reservoir.

A somewhat similar device is described by Giezen et al in U.S. Pat. No.4,154,107. The device utilizes an activator acid in a pressure sensitiveadhesive which migrates to contact an organic dye producing anaqueous-mediated color change. The preferred device also requires anabsorbant paper element to contain the indicator and a wetting agent toretain water to introduce color change. The activating/indicatingcomponents used in the device are water soluble and hence theperformance of the device is adversely affected by moisture andhumidity. In order to protect the device, an enveloping plastic film isemployed.

Kydonieus et al in U.S. Pat. No. 4,212,153 describe a device formonitoring product shelf life in which a dye preferably migrates from alower plastisol layer to an upper indicator layer, being preferablypolyvinylchloride. The device can also utilize a barrier film tointroduce an induction period to color change, but doesn't describe atape device, or the separate use of an activator and indicator agent.

Bradley et al in U.S. Pat. No. 4,292,916 describe a tape device formonitoring shelf life which involves the migration of a dye from acarrier layer to a transfer layer to highlight a message. However, thedevice preferably uses a porous barrier such as cheese cloth, requires aprotective cover, does not describe the use of pressure sensitiveadhesives to bond the different layers of the device together andrequires an impervious covering layer for the entire indicator device.

U.S. Pat. No. 3,520,124 to Myers describes a device to indicate apredetermined time interval based on two or more materials which react,either chemically or physically over a predetermined period to produce atermination signal. The reacting materials are carried on a base memberand are separated by a barrier preventing contact. Upon elimination ofthe barrier, a commencement signal is produced indicating the timereaction is underway. However, there is not described a tape device orthe use of pressure sensitive adhesives for bonding the layers of thedevice together.

Other patents in the art include: U.S. Pat. Nos. 3,677,088; 3,967,579;3,360,338; 4,057,029; 3,065,083; 4,188,437; 2,889,799; 3,078,182;3,311,084; 3,386,807; 4,154,107.

Also described in the art are "moving boundary" devices which operate onthe principle of a moving band of produced color so that thecontinuously elapsed time of the monitored period can be visuallyobserved. They are described in U.S. Pat. Nos. 4,382,700; 4,196,057;4,196,055; 4,432,656; 2,614,430; 3,479,877; 3,414,415; 3,942,467;3,954,011; 3,981,683; 4,057,029; 4,163,427; 4,280,441; 4,410,493;4,509,449.

Many of the above referred-to devices use liquids or vapors as theactivator in the color-indicating systems rather than a solidwater-impermeable material which is required in a tape. Further thereferences do not specifically teach one skilled in the art how todesign a particular tape device in order to match the product decaycharacteristics particularly with respect to the Eact and the rateconstant to accurately monitor the perishable product over a range ofstorage temperature conditions.

SUMMARY OF THE INVENTION

We have found that an accurate color changing device for measuring thetime-temperature history and remaining shelf-life of a perishableproduct can be constructed by matching the product decay Arrheniuscharacteristics with the color change Arrhenius characteristics of theindicator. This is done by employing an activator-indicator system inwhich the activator and indicator are separately contained in matrixlayers, optionally employing a barrier matrix layer, which aresandwiched together by means of at least one pressure sensitive adhesiveand which allow the migration of the activator through the barrierand/or indicator matrix. The diffused activator reacts with theindicator to produce a color change. The rate of color production isselected to match the product decay rate in the temperature range ofinterest, generally being the storage temperature. This is done byselecting the matrix layers and optionally the barrier layer to producean activator-indicator system that exhibits the same slope, i.e.activation energy, and apparent extrapolated rate constant, i.e.Y-intercept, in the desired temperature range. By use of this technique,color changing devices can be constructed to monitor a wide range ofperishable products and particularly including foods which aresusceptible to thermal degradation.

By this invention there is provided a device for monitoring thetime-temperature storage history of a perishable product having ameasurable activation energy of product deterioration comprising:

a) an indicator tape comprised of a transparent polymer film and affixedthereto at least one water-impermeable matrix layer containing anindicator composition:

b) an activator tape comprised of a substrate and affixed thereto atleast one water-impermeable matrix layer containing, in solid solution,an activator composition:

c) a composite barrier matrix, said indicator tape and activator tapematrix layers, bonded together by at least one pressure sensitiveadhesive; said activator composition being capable of diffusing throughsaid composite matrix in a predetermined time to contact said indicatorcomposition producing a visually observable color change in saidindicator composition; said device being substantially impermeable tomoisture, and said device possessing an activation energy and rateconstant for color change which are substantially the same as theactivation energy and rate constant for product deterioration of theperishable product in the temperature region of monitoring.

One of the simplest form of the color changing device is shonschematically in FIG. 3, wherein said indicator tape matrix layer (a)and said activator tape matrix layer (b) are adhered together to form auniform thickness composite matrix (c).

In order to introduce an induction period for the color change and varythe activation energy, a barrier matrix layer of uniform thickness canbe placed between both matrix layers as shown schematically in FIG. 4.

Alternatively, the barrier layer of uniform thickness can be coated onthe indicating matrix as shown schematically in FIG. 5.

In order to prevent, migration of the indicator, the barrier layershould, preferably, be essentially impermeable to the indicatingcomposition. The matrix of the barrier layer could be the same as thatof indicating or activating layer, or could be an entirely differentmatrix.

Another embodiment is where the device is characterized in having anactivation energy and rate constant of color change which issubstantially the same as the activation energy and rate constant forproduct decay of the perishable product in the temperature region ofmonitoring.

Also provided is a process for measuring the shelf life of a perishableproduct comprising the step of affixing to said product the devicedescribed above and activating the device.

Further provided is a perishable product having the device describedherein, in inactivated or activated form, attached thereto.

Still further provided is a process for constructing the devicedescribed herein for measuring the shelf life of a perishable productcomprising the step of laminating:

a) an indicator tape comprised of a transparent polymer film and affixedthereto, at least one matrix layer containing an indicator composition;and

b) an activator tape comprised of a substrate and affixed thereto atleast one matrix layer containing an activator composition in solidsolution; producing a composite matrix layer wherein said activatorbeing capable of permeating through said barrier at a predetermined timeto contact said indicator producing a visually observable color changein the indicator tape.

Also provided is the above-described device which is activated bythermal annealing, ultraviolet radiation or applied pressure.

Furthermore there is provided a device for measuring the shelf-life of aperishable product having a measurable activation energy of productdeterioration comprising:

a) an indicator tape comprised of a transparent polymer film and affixedthereto at least one water-impermeable matrix layer containing anindicator composition:

b) an activator tape comprised of a substrate and affixed thereto atleast one water-impermeable matrix layer containing in solid solution anactivator composition:

c) a composite matrix, comprised of a plurality of laminated matrixlayers, including said indicator tape and activator tape matrix layers,bonded together by at least one pressure sensitive adhesive, and saidactivator composition is capable of diffusing through said compositematrix in a predetermined time to contact said indicator compositionproducing a visually observable change in predetermined time influorescence of said indicator composition.

Also provided is a device for measuring the shelf-life of a perishableproduct having a measurable activation energy of product deteriorationcomprising:

a) an indicator tape comprised of a transparent polymer film and affixedthereto at least one water-impermeable matrix layer containing anindicator composition:

b) an activator tape comprised of a substrate and affixed thereto atleast one water-impermeable matrix layer containing in solid solution anactivator composition:

c) a composite matrix, comprised of a plurality of laminated matrixlayers, including said indicator tape and activator tape matrix layers,bonded together by at least one pressure sensitive adhesive, and saidactivator composition is capable of diffusing through said compositematrix in a predetermined time to contact said indicator compositionproducing a measurable change in the electrical conductance of saidindicator composition.

There is furthermore provided a device for monitoring thetime-temperature storage history of a perishable product having ameasurable activation energy of product deterioration comprising:

a) an indicator tape comprised of a transparent polymer film and affixedthereto at least one water-impermeable matrix layer containing anindicator composition positioned below an opaque additive:

b) an activator tape comprised of a substrate and affixed thereto atleast one water-impermeable matrix layer containing in solid solution anactivator composition capable of dissolving said opaque additive:

c) a composite matrix, comprised of a plurality of laminated matrixlayers, including said indicator tape and activator tape matrix layers,bonded together by at least one pressure sensitive adhesive, and saidactivator composition is capable of diffusing through said compositematrix in a predetermined time to contact and dissolve said opaqueadditive, producing a visually observable change in said indicatorcomposition.

Further there is provided a process for altering the activation energyof the above-described device to match that of the perishable productcomprising the step of varying the nature of one of the followingcomponents of the device selected from: activator matrix, indicatormatrix, barrier matrix, activator, indicator, additives in a matrix,interface between two matrices, the degree of crystallinity of a givenmatrix, or combination of said components.

DESCRIPTION OF THE FIGURES

FIG. 1 illustrates a hypothetical Arrhenius kinetics diagram for aperishable B and indicator A being non-parallel (different Eact's) buthaving a common process rate at Ti, and indicator C being parallel to B(same Eact's) but with no common reaction rate constant.

FIG. 2 illustrates kinetics diagrams for various common perishable foodsillustrating relative stabilities, i.e. shelf-lives, at differenttemperatures.

FIG. 3 is a schematic cross sectional view of a two-layer device inwhich:

(a) is the indicator tape comprised of plastic film 1, having a uniformthickness matrix layer 9, containing indicator 3;

(b) is the activator tape comprised of plastic film 4, having auniformed thickness matrix layer 10, containing activator 6 in solidsolution and an adhesive layer 7;

(c) is the activated device obtained by the lamination of the indicatormatrix onto the activator matrix forming the composite matrix.

FIG. 4 is a schematic cross sectional view of a three-layer devicecontaining a barrier layer matrix of uniform thickness in which:

(a) is the indicator tape comprised of plastic film 1, having an adheredmatrix layer 2, containing indicator 3;

(b) is the barrier matrix layer 11 of uniform thickness;

(c) is the activator tape comprised of plastic film 4, having a uniformthickness matrix layer, 10 containing activator 6 in solid solution andan adhesive layer 7;

(d) is the activated device obtained by laminating the barrier matrixlayer between the indicator tape and activator tape matrices.

FIG. 5 is a schematic cross sectional view of another embodiment of athree-layer device employing a uniform thickness middle barrier matrixlayer applied on the activator tape in which:

(a) is the indicator tape comprised of plastic film 1, having a matrixlayer 2, containing indicator 3, and an attached, laminated, uniformthickness barrier layer matrix 8;

(b) is the activator tape comprised of plastic film 4, having a matrixlayer 5, containing activator 6 in solid solution, and an adhesive layer7;

(c) is the activated device obtained by lamination of the indicatormatrix (and the barrier matrix) onto the activator matrix.

FIG. 6 is an Arrhenius kinetic diagrams:

(a) showing the variation in the rate constants of hypothetical deviceshaving the same activation energy;

(b) showing the variation in the activation energies of hypotheticaldevices.

FIGS. 7-12 illustrate the alteration of the activation energy in atheinvention device by suitable changes in the nature of the individualcomponents.

BRIEF DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

The device can best be described by reference to the Figures. Referringto FIG. 3, substrate 1, a piece of transparent plastic film, is coatedwith a matrix 9 such as an adhesive, containing a known concentration ofan indicator 3. This tape of FIG. 3a is referred hereafter to as the"INDICATOR TAPE". Similarly, substrate 4, a flexible substrate, iscoated with a matrix 10, containing an activator 6, in solid solution,as shown schematically in FIG. 3b. By the term "solid solution" is meantthat the activator is completely dissolved and uniformlydissolved/dispersed throughout the activator matrix layer. This tape ofFIG. 3b is referred hereafter to as "ACTIVATOR TAPE". The matrices 9,and 10 can be the same or different. Both matrices must bewater-impermeable and one of the matrices should preferably be apressure sensitive adhesive and have an ability to form an adhesive bondwith the other matrix.

If both the substrates, 1 and 4, are transparent, either one of them canbe applied to perishable container. The substrate contacting theperishable container is referred to hereinafter as the base substrate orbase film and is preferably the activator substrate. The base film maypreferably have another adhesive backing 7, so that the device can beapplied to a perishable container. The adhesive 7 does not contain anactivator or indicator. The activator film 4 can be transparent oropaque (e.g. metal foil) but the top (indicator) film 1 must betransparent, so that the color change can be visually observed. When theactivator reacts with the indicator, it produces a visually observablecolor change, which is essentially simultaneously over the surface ofthe indicator, unless the indicator is in the form of a bar code oralphanumeric symbol.

The device is activated by laminating the indicator tape to theactivator tape so that the indicator matrix contacts the activatormatrix as shown in FIG. 3c. As one of the matrices is an adhesive, e.g.pressure sensitive adhesive, a moderately applied pressure will form aneffective bond between them. Once the device is activated, the twomatrix layers form a composite layer (film). The term "ACTIVATION" isused to describe the process of adhering indicator tape of FIG. 3a tothe activator tape of FIG. 3b to form the reactive (color changing)device of FIG. 3c, which is referred hereinafter to as "TAPE DEVICE".

Once the device is activated, the solid solution activator 6 willmigrate into the indicator matrix 9, where it will react with theindicator 3 and introduce a color change. The indicator display can be aprinted message.

The color changing device of the instant invention can have manymodifications and embodiments, which are presented below:

The three layer device of FIG. 5 is comprised of three parts, theindicator tape (a), the activator tape (b), and a barrier matrix layer8, adhered to the indicator tape. The barrier matrix layer can beapplied to either indicator or activator tape to form the compositematrix at the time of activation for end use. A transparent plastic film1, is coated with the matrix medium 2, containing a known concentrationof an indicator 3 adhered to the barrier matrix 8, as shownschematically in FIG. 5a to form the indicator tape. Similarly, a pieceof flexible substrate 4, is coated with an matrix 5, containing anactivator 6, in solid solution, as shown in FIG. 5b to form theactivator tape. This tape is similar to that shown in FIG. 3b. Thebarrier layer 8 can be coated onto matrix 5 as well. The matrices 2, 5and 8 can be of the same or different compositions, and preferably atleast one is a pressure sensitive adhesive. The base film 4 may haveanother adhesive backing 7, so that the device can be applied to aperishable container. The device is activated by laminating theindicator tape onto the activator tape as shown in FIG. 5-C. Once thedevice is activated, the three layers form a composite layer. Theactivator will diffuse through the barrier matrix into the indicatormatrix where it will react with the indicator and introduce a colorchange.

Alternatively, the barrier layer of uniform thickness matrix ofdifferent permeabilities can be coated on the indicator matrix as shownin FIG. 4. Thus the three layer device becomes two layer device.

Another modification of the device of either FIGS. 3-5 is to coat orprint the indicator in form of message. Instead of the continuouscoating of the indicator, one can coat or print the indicator in form ofa message, e.g. IF THIS IS RED, DO NOT USE. In such case, only themessage will gradually appear or undergo the color change.

Another modification of the basic device is to coat or print theindicator in form of bar codes. Instead of the continuous coating of theindicator, one can coat or print the indicator in form a of bar code. Inthis case, only the bars will undergo the color change and aconventional bar code reading apparatus can be used to read shelf lifeof the perishable. Other product information, such as inventory control,can also be combined into the bar codes.

The device can also be prepared and activated on perishable productionline. For example, perishable containers can be printed with anindicator. The coating (layer) of activator can be applied at the timeof top coating to activate the device at the time of filling thecontainer with the perishable.

The indicator tape and activator tape can be prepared in the form of bigrolls and stored separately essentially indefinitely. The rolls cansubsequently be loaded onto a particular processing machine/equipment.In order to activate the device, the rolls will laminate the activatortape onto the indicator tape (with a barrier film in between ifrequired), cut to the desired size and applied to the perishable.Commercially available equipment for lamination and application oflabels which are conventional can be combined and modified foractivation and application of the device on line.

The size of the device can be as small as a few millimeters to severalcentimeters or larger, if desired. The thickness of the device typicallycan be from a thousandth of a centimeter to a millimeter, or thicker, ifdesired.

The indicator and activation tapes can be prepared by coating themixture of indicator (and activator) and matrix on a substrate. Coatingis an old and well developed technology. A variety ofprocesses/equipment have been developed for coating adhesives, inks,laquers, and other polymeric materials. Common coating methods are: airknife, brush, calender, cast coating, curtain, dip, extrusion, blade,floating knife, gravure, kiss roll, off-set, reverse roll, rod, spray,and squeeze roll. These methods have been reviewed by Coeling, andBublick (K. J. Coeling, and T. J. Bublick, Encycl. Polym. Sci. Eng.,Vol. 3, 552-615, 1986). Most of the above methods can be used forcoating the matrix on a wide range of base materials.

The device can be activated by lamination of the activator tape with theindicator tape. Lamination is a process of uniting two or more layers ofdifferent or similar materials into one composite layer by the action ofheat or pressure. Since one of the substrates is coated with anadhesive, preferably a pressure sensitive adhesive, it can be laminatedwith the other substrate by application of moderate pressure, or heat.In a perishable product, packaging plant, the devices can be activatedby lamination and applied directly onto the containers.

The device can be printed in form of bar codes. "Bar coding" is used totrack inventory in the warehouses and to read prices of foods insupermarkets. Bar coding is a technique for automated data collection. Abar code is a series of black bars and spaces which represent lettersand/or numerals. (See P. E. Boyle, Barcode News, November 1985). Todecode the information in a bar code, a small spot of light is passedover the bars and spaces via a scanning device. The bar code willreflect the light back into the scanner in various amounts. Thesedifferences in reflections are translated into electrical signals by alight detector inside the scanner. The signals are converted into binaryzeroes and ones which are used in various combinations to stand forspecific numbers and letters.

The basic components of the device and their functions are describedbelow:

The indicator film 1 can be any transparent plastic film being waterimpermeable on which a matrix such as an adhesive or ink can be coated.It should preferably be clear in order to observe the color change ofthe indicator. Representative examples include a large number of plasticfilms including those made from polyethylene, polypropylene, cellulosederivatives such as cellulose acetate, polyesters such as poly(ethyleneterephthalate), polyamides such as nylon-66, polyurethanes,polyvinylchloride, and polycarbonates such as poly(bisphenol-Acarbonate). Preferred indicator films are polyethylene, polypropylene,cellulose acetate, poly(ethylene terephthalate), polyvinylchloride andmultilayer laminated films, preferably comprising a composite ofpolyethylene, polyethylene terephthalate and polyvinylchloride .

The activator tape base film 4 can be any transparent or opaque plasticfilm or metal foil being water-impermeable on which a matrix such as anadhesive can be coated on both the sides. Once the device is assembled,this tape is applied to the perishable container. Aluminium foil and theplastic films listed above for the indicator film can be used.

Preferred activator films are aluminum, polyethylene, polypropylene,cellulose acetate, poly(ethylene terephthalate), polyvinylchloride andmultilayer laminated films, preferably comprising the compositedescribed above.

The indicator, activator and barrier layer matrix materials can be anywater-impermeable polymeric material suitable for incorporating avariety of inks, paints or adhesives which are preferably transparentand in which an activator and indicator can be incorporated. At leastone matrix is preferably a pressure sensitive adhesive. General classesof polymers suitable for activator and indicator matrix include resinssuch as epoxy, phenol-formaldehyde, amino-formaldehyde, polyamides,vinyls, acrylics, polyurethanes, polyesters, water soluble resins,alkyds, elastomers, and rosins. Some of them are listed in the followingreferences, "Resins for Surface Coatings", P. Oldring and G. Hayward,and "Resins and Varnishes for Ink and Paint", both published by McNairPublications, New York, N.Y.

Pressure sensitive adhesives (see "Handbook of Pressure SensitiveAdhesives Technology" by Don Schar (Ed,), Van Nostrand N.Y., 1982) are apreferred matrix layer. Included are pressure sensitive adhesives havingan elastomer or rubbery polymer as the elastic component and a lowmolecular weight tackifying viscous component. Common rubber basedpressure sensitive adhesives include natural elastomers, syntheticelastomers such as polychloroprene, polyurethane, and random and blockcopolymers of styrene-butadiene, styrene-isoprene, polyisobutylene,butyl rubber, and amorphous polypropylene. These are compounded withtackifying resins to formulate hot melt pressure sensitive adhesives.Common acrylic adhesives such as polymers of 2-ethylhexylacrylate, butylacrylate, ethylacrylate, and acrylic acid. These acrylic adhesives areinherently pressure sensitive. Polymers and copolymers of vinyl etherssuch as vinylmethylether, vinylethylether and vinylisopropylethers areused as pressure sensitive adhesives. Two types of silicone gums; 1) allmethyl based and 2) the phenyl modified can also be used as pressuresensitive adhesives. The silicone resin is used as a tackifier and byadjusting the resin to gum ratio, they can be made with a wide range ofadhesion properties. High silicone gum content adhesives are extremelytacky. Silicone adhesives are also crosslinked (cured) by catalysts suchas benzoyl peroxide and amino silane.

In order to print a bar code or message, an ink form of the matrix ismore convenient than an adhesive. Useful herein are a variety of inkssuch as flexo, gravure, off-set, letter press, and litho which are usedfor printing. Inks are composed of three basic components, vehicle(solvent), pigment (color) and binder (polymer). The ink (matrix) forthe device can be composed of the similar three basic ingredients,indicator (pigment), solvent (vehicle) and matrix (binder) such ascellulose nitrate, rosin esters, acrylate and vinyl polymers,polyesters, polyamides and polyepoxy.

The barrier layer material for devices of FIGS. 4-5, as described above,can be any polymeric material in which the activator can diffusethrough, but inhibits any significant diffusion by the indicator. Thebarrier material can be an adhesive, ink or a plastic film as describedabove.

Preferred barrier materials are polyethylene, polypropylene, celluloseacetate, poly(ethylene terephthalate), polyvinylchloride, epoxy,phenol-formaldehyde, amino-formaldehyde, polyamides, vinyls, acrylics,polyurethanes, polyesters, silicone resins, water soluble resins,alkyds, synthetic and natural elastomers, and rosins.

The function of the barrier matrix layer is twofold, to increase thetime for color change, i.e., rate constant, and also to alter theactivation energy of the device.

The activator-indicator compositions can be any two compounds whichinteract by a physical or chemical reaction to produce an observablecolor change or measurable physical characteristic. The activator andindicator can be solid or liquid. The activator should dissolve in, i.e.form a solid solution with, its matrix and must be able to migrate outof the activator matrix. The indicator and activator can be one compoundor a mixture of two or more compounds including catalyst or reactionmedium.

A large number of reactions are associated with color changes. In eachtype of color changing reaction there are several classes of compoundsand each such class has several compounds which undergo a color change.Below are some type of reactions and classes of compounds which can beused as indicators and activators in the invention device.

Color changing reactions and indicators are used for detection andmonitoring of organic, inorganic and organometallic compounds. Suchcolor changing reactions and compounds are listed in a large number ofbooks, reviews and publications, including those listed in the followingreferences: Justus G. Kirchner, "Detection of colorless compounds", ThinLayer Chromatography, John Wiley & Sons, New York, 1976; E. Jungreis andL. Ben. Dor., "Organic Spot Test Analysis", Comprehensive AnalyticalChemistry, Vol. X, 1980; B. S. Furniss, A. J. Hannaford, V. Rogers, P.W. Smith and A. R. Tatchell, Vogel's Textbook of Practical OrganicChemistry, Longman London and New York, p. 1063-1087, 1986; Nicholas D.Cheronis, Techniques of Organic Chemistry, Micro and Semimicro Methods,Interscience Publishers, Inc. New York, 1954, Vol. VI, p. 447-478; HenryFreiser, Treatise on Analytical Chemistry, John Wiley and Sons, NewYork-Chinchester-Brisbane-Toronto-Singapore, 1983, Vol. 3, p. 397-568;Indicators, E. Bishop (Ed.), Pergamon Press, Oxford, U.K., 1972. Thesereactions and compounds can be used in the device for recordingtime-temperature history. Listed below are representative classes ofreactions and compounds that can be used in the device.

Oxidizing agents can oxidize reduced dyes and introduce a color change.Similarly, reducing agents can reduce oxidized dyes and introduce acolor change. For example, ammonium persulfate can oxidize colorlessleucocrystal violet to violet colored crystal violet. Reducing agentssuch as sodium sulfite can reduce crystal violet to leucocrystal violet.Thus oxidizing and reducing agents can be used as activators withappropriate redox indicators, in the invention device.

Representative common oxidants (oxidising agents) include: ammoniumpersulfate, potassium permanganate, potassium dichromate, potassiumchlorate, potassium bromate, potassium iodate, sodium hypochlorite,nitric acid, chlorine, bromine, iodine, cerium(IV) sulfate, iron(III)chloride, hydrogen peroxide, manganese dioxide, sodium bismuthate,sodium peroxide, and oxygen. Representative common reducing agentsinclude: Sodium sulfite, sodium arsenate, sodium thiosulfate, sulphurousacid, sodium thiosulphate, hydrogen sulfide, hydrogen iodide, stannouschloride, certain metals e.g. zinc, hydrogen, ferrous(II) sulfate or anyiron(II) salt, titanium(III) sulphate, tin(II) chloride, tin(II)chloride and oxalic acid. The following table provides somerepresentative preferred oxidation-reduction indicator combinations andtheir respective color changes:

                  TABLE 1                                                         ______________________________________                                        Representative oxidation reduction indicators and their                       color changes.                                                                               Color change                                                   Indicator        Oxidized form                                                                             Reduced form                                     ______________________________________                                        5-Nitro-1,10-phenanthroline                                                                    Pale blue   Red                                              iron(II) sulphate (nitroferroin)                                              1,10-Phenanthroline iron(II)                                                                   Pale blue   Red                                              sulphate(ferroin)                                                             2,2'-Bipyridyl iron(II) sulphate                                                               Faint blue  Red                                              5,6-Dimethylferroin                                                                            Pale blue   Red                                              N-phenylanthranilic acid,                                                                      Purple red  Colorless                                        4,7-Dimethyl-1,10-                                                                             Pale blue   Red                                              phenanthroline iron(II)                                                       sulphate (4,7-dimethylferroin)                                                Starch-KI        Blue        Colorless                                        Methylene blue   Blue        Colorless                                        Diphenylaminesulphonic acid                                                                    Red-violet  Colorless                                        Diphenylbenzidine                                                                              Violet      Colorless                                        Diphenylamine    Violet      Colorless                                        3,3'-Dimethylnaphthidine                                                                       Purplish-red                                                                              Colorless                                        All leuco dyes   color       Colorless                                        ______________________________________                                    

Acid-base reaction are colorless, but can be monitored with pH sensitivedyes. For example, bromophenol blue when exposed to a base such assodium hydroxide turns blue. When blue-colored bromophenol blue isexposed to acids such as acetic acid it will undergo a series of colorchanges such as blue to green to green-yellow to yellow. Thus, acids andbases can be used as activators and corresponding pH dyes as indicators.

The following are representative examples of dyes that can be used fordetection of bases: Acid Blue 92; Acid Red 1, Acid Red 88, Acid Red 151,Alizarin yellow R, Alizarin red %, Acid violet 7, Azure A, Brilliantyellow, Brilliant Green, Brilliant Blue G, Bromoscresol purple, Bromothymol blue, Cresol Red, m-Cresol Purple, o-Cresolphthalein complexone,o-Cresolphthalein, Curcumin, Crystal Violet, 1,5-Diphenylcarbazide,Ethyl Red, Ethyl violet, Fast Black K-salt, Indigocarmine, Malachitegreen base, Malachite green hydrochloride, Malachite green oxalate,Methyl green, Methyl Violet (base), Methylthymol blue, Murexide,Naphtholphthalein, Neutral Red, Nile Blue, alpha-Naphthol-benzein,Pyrocatechol Violet, 4-Phenylazophenol, 1(2-Pyridyl-azo)-2-naphthol,4(2-Pyridylazo) resorcinol Na salt, auinizarin, Quinalidine Red, ThymolBlue, Tetrabromophenol blue, Thionin and Xylenol Orange.

The following are representative examples of dyes that can be used fordetection of acids: Acridine orange, Bromocresol green Na salt,Bromocresol purple Na salt, Bromophenol blue Na salt, Congo Red, CresolRed, Chrysophenine, Chlorophenol Red, 2,6-dichloroindophenol Na salt,Eosin Bluish, Erythrosin B, Malachite green base, Malachite greenhydrochloride, Methyl violet base, Murexide, Metanil yellow, MethylOrange, Methyl violet base, Murexide, Metanil yellow, Methyl Orange,methyl Red Sodium salt, Naphtho-chrome green, Naphthol Green base,Phenol Red, 4-Phenylazo-aniline, Rose Bengal, Resazurin and2,2'4,4',4"-Pentamethoxytriphenylmethanol.

Organic chemicals can be detected by the presence of their functionalgroups. Organic functional group tests are well known and have beendeveloped for the detection of most organic functional groups, and canbe used as the basis for the indicator-activator combination. Forexample, ceric nitrate undergoes a yellow to red color change when itreacts with an organic compound having aliphatic alcohol (--OH) asfunctional group.

Organic compounds having one or more of the following representativefunctional groups can be used in the device as activators: alcohols,aldehydes, allyl compounds, amides, amines, amino acids, anydrides, azocompounds, carbonyl compounds, carboxylic acids, esters, ethoxy,hydrazines, hydroxamic acids, imides, ketones, nitrates, nitrocompounds, oximes, phenols, phenol esters, sulfinic acids, sulfonamides,sulfones, sulfonic acids, and thiols.

There are thousands of compounds under each functional group classlisted above. For example, the following is a representative list ofaminoacids that can be used as activators in the device: alanine,arginine, aspartic acid, cysteine, glutamic acid, glycine, histidine,hydroxylysine, lysine, methionine, phenylalanine, serine, tryptophan,tyrosine, alpha-aminoadipic acid, alpha, gamma-diaminobutyric acid,ornithine and sarcosine.

All alpha-amino acids undergo a colorless to purple-violet color whenreacted with ninhydrin. In addition, the following are some specificamino acid tests: 1) Diazonium salts couple with aromatic rings oftyrosine and histidine residues to produce colored compounds. 2)Dimethylaminobenzaldehyde condenses with the indole ring of tryptophanunder acid conditions to form colored products. 3) alpha-Naphthol andhypochlorite react with guanidine functions (arginine) to give redproducts.

The following is a representative list of alpha-amino acids that can beused as solid amines: Lysine, hydroxylysine, alpha, gamma-diaminobutyric acid and ornithine.

The following are some further selected examples of organic compoundsthat undergo a color change in the presence of a functional group testreagent:

Primary, secondary and tertiary aliphatic and aromatic amino bases canbe detected with 2,4-dinitro chlorobenze. The observed color change isfrom colorless to yellow-brown.

Aliphatic amines, primary aromatic amines, secondary aromatic amines andamino acids react with furfural in glacial acetic acid to give violetSchiff bases.

A variety of triphenylmethane dyes react with sulfurous acid to producea colorless leuco sulfonic acid derivative. When this derivative isallowed to react with an aliphatic or aromatic aldehyde, coloredproducts are obtained.

Fuchsin, decolorized with sulfite when exposed to aliphatic and aromaticaldehydes, gives a violet blue color.

Malachite green, decolorized with sulfite when exposed to aliphatic andaromatic aldehydes, gives a green color.

Proteins and primary or secondary amines react with ninhydrin and manyother stains to form colored products [Conn's Biological Stain, R. D.Lillie (Ed.), Williams and Wilkinson Company, 1977].

Guanidino Compounds react with a mixture of diacetyl and calcium oxideto give a red colored product.

A mixture of ferrous ammonium sulfate and potassium fluoride in diluteacid gives a yellow-orange to red-violet color when reacted withalpha-carboxylic acids of aromatic heterocyclic bases.

Ensols give a red color with neutral ferric chloride. Ensols give agreen or blue copper derivative when reacted with copper II acetate.

A benzene solution of an acidic compound reacts with a mixture ofRhodamine B and 1% uranylacetate to give red or pink colored products.

A mixture of acidic compound, 2% iodide and 4% iodate when heated andexposed to starch or thyodene indicator gives a blue to violet color.

Organic oxidants which are active in neutral media can be detected bythe yellow-brown color it produces with thio Michler's ketone(4-4'-bis-dimethylamino thio benzophenone). Organic oxidants react witha colorless tetrabase, i.e., tetramethyldiaminodiphenylmethane, to givea blue color.

A neutral or acidic solution of a reducing agent is reacted with aqueousphosphomolybdic acid and concentrated ammonic to give a blue-greencolor.

Test methods are also well known for the detection of inorganiccompounds, their cations and anions, which are associated with a colorchange. These reactions and corresponding compounds can also be used inthe device. Inorganic compounds and indicators for their detection aredescribed in references: J. Bassett, R. C. Denney, G. H. Jeffery and J.Mendham, Vogel's Textbook of Quantitative Inorganic Analysis, LongmanScientific and Technical, p. 294, 1986.; Fritz Feigl, Vinzenz Anger andRalph E. Oesper, Spot Test in Inorganic Analysis, Elsevier PublishingCompany, 1972, p. 526-616.; Products for Analysis, Catalog of HachCompany, 1986-87. Representative examples of color changing reactions ofinorganic cations and anions are listed below:

Cations: Aluminum ion reacts with alizarins to give a red precipitate;ammonium ion gives a red color with p-nitrobenzenediazonium chloride;copper ions react with cuproine to give a pink purple color; ferrous iongives a red color with 2,2'-dipyridyl; ferric ion reacts with potassiumferrocyanide to give a blue color; magnesium ion gives a blue color withmagneson; nickel ion reacts with dimethylglyoxime to give a red color;sodium ion gives a yellow color with zinc uranyl acetate; zinc ionreacts with dithizone to give a red color.

Anions: Acetate ion reacts with a mixture of lanthanum nitrate andiodine to give a blue color; bromide ion gives a red color withfluorescein; ferrocyanide reacts with ferric chloride to give a bluecolor; fluoride ion gives a pink color which turns yellow when reactedwith a mixture of zirconium-alizarin; iodides react with nitroprussideto give a red color; thiocyanate ion reacts with ferric chloride to givea red color.

The synthesis of dyes generally involves the reaction between two ormore colorless intermediates to produce a colored product (references R.L. M. Allen, Color Chemistry, Appleton-Century, Crofts, 1971; K.Venkatraman, The Chemistry of Synthetic Dyes, Vol. II, Academic Press,New York, 1952). Often, mild reaction conditions are used. Some typicalexamples of dye syntheses are as follows: (1) Indophenol Blue: Thereaction of alpha-naphthol with p-nitroso-dimethylaniline in thepresence of acid gives indophenol blue. (2) Yellow Couplers:Benzoylacetanilides react with N,N'-dialkyl-p-phenylenediamine in thepresence of silver ions to afford yellow azamethine dye. (3) Azo Dyes:Benzoisooxazolones give yellow azo dyes when reacted with N,N'dialkyl-p-phenylenediamine. (4) Magenta Dyes: Pyrazolone couplers reactwith N,N' dialkyl p-phenylenediamine in the presence of silver bromideto give magenta azamethine dye. (5) Pyronine Group: The condensation oftwo moles of m-dialkylamino phenol with an anhydride of a dicarboxylicacid in the presence of a mineral acid gives the Pyronine group of dyesviz. Rhodamine S. (6) Triphenylmethane derivative: Reaction ofo-chlorobenzaldehyde with 2-methyamino-p-cresol gives a brilliant reddye, Rhodamine 5G. (7) Pigments: Condensation of 4,5,6,7tetrachloroiso-indolin-1-one with aromatic amines give rise to pigmentscalled Irgazine. These pigments vary in color from yellow, orange, redand brown depending on the aromatic amine.

Several rearrangement reactions are known in organic chemistry (AdvancedOrganic Chemistry, Third Edition, Jerry, March, p. 942-1047). Some ofthese rearrangements are: Pinacol Rearrangement, Dienone-PhenolRearrangement, Wallach Rearrangement, Fischer-Indole Synthesis,Favoroski Type Rearrangements, Curtius Rearrangement, LossenRearrangement. Some of the compounds involved in these rearrangementreactions can be used for preparation of the device. An example of arearrangement reaction is the pinacol rearrangement where 1,2 vic-diols,when reacted with a mineral acid, rearrange to form either an aldehydeor ketone which in turn can be detected with 2,4-dinitrophenylhydrazine.

Some of the above mentioned rearrangement reactions are also known asOrganic Name Reactions. There are several other organic name reactionsknown (The Merck Index, Tenth Edition, pp. ONR-1 to ONR-100). Some ofthese name reactions are: Bayer-Drewson Indigo Synthesis, BaudischReaction, Meisenheimer Complexes, Rosenheim Color Test, ZimmermanReaction. An example of a reaction involving two reactants A and B toproduce a colored product C is the Baudisch Reaction whereO-nitrosophenol reacts with a copper salt, to give a colored product.

A large number of adsorption indicators are known (Indicators, EdmundBishop, Pergaman Press 1972, Ch 7 p. 437-468). some of these indicatorsalong with the ions responsible for the color change can be used in thedevice. Table 2 below lists some ions, indicators and associated colorchanges (ppt. indicates precipitate):

                  TABLE 2                                                         ______________________________________                                        A representative list of ions useful as activators and                        corresponding indicators and color changes.                                   Ions       Indicator      Color Change                                        ______________________________________                                        Ag+ with Br.sup.-                                                                        Rhodamine 6G   pink → violet                                Ag.sup.+ Br.sup.-                                                                        Phenosafranine Blue → Red.                                  Cl.sup.- Br.sup.-,I.sub.-                                                                Fluorescein    Yellow green → Pink                          Cl.sup.-,Br.sup.- Ag.sup.+                                                               Phenosafranine Red → Blue                                   I.sup.-  Ag.sup.+                                                                        Erythrosin     Yellowish → Reddish                                                    Red → Violet                                 Scn.sup.- Ag.sup.+                                                                       Alizarin Red   Yellow → Red                                            Aurazine       Green → Orange Red                                                     Fluor. → Fluor.                              Scn.sup.- (Ag.sup.+)                                                                     Dichloro(R)-Fluoresin                                                                        Yellow green → Red                                      Eosin          Pink → Red-Violet                                       Rose Bengal    Red → Purple                                            Tartrazine     Colorless → Green                            Zn[Fe(CN.sub.6).sub.4.sup.- ]                                                            Methyl Red     Pink → Yellow                                Hg.sub.2.sup.2+  (cl + Br)                                                               Diphenylcarbazide                                                                            Bluish → Colorless                           ______________________________________                                    

A large number of reactions are assembled with a change in fluorescencerather than a color change in the visible region. Such compounds can beused as indicator/activator pairs in the device. The time-temperaturehistory and thus shelf life can be monitored by monitoring the change influorescence. Several fluorescent indicators are known (Vogel's Textbookof Quantitative Inorganic Analysis, Fourth Edition, Longman, p. 776.)and some of these along with their respective color change are listed inTable 3 below:

                  TABLE 3                                                         ______________________________________                                        A representative list of fluorescent dyes and their color                     changes                                                                       Indicator        Color Change                                                 ______________________________________                                        Acridine         Green-to-violet blue                                         2-Hydroxycinnamic acid                                                                         Colorless-to-green                                           3,6-Dihydroxyphthalimide                                                                       Colorless-to-Yellowish Green                                 Eosin            Colorless-to-green                                           Erythrosin B     Colorless-to-green                                           Fluorescein      Colorless-to-green                                           4-Methyl-Aesculetin                                                                            Colorless-to-blue                                            2-Naphthoquinoline                                                                             Blue-to-colorless                                            Quinine sulfate  Blue-to-violet                                               Quininic Acid    Yellow-to-blue                                               ______________________________________                                    

The device and its modifications are not limited to activator--indicatorcombinations which are associated with chemical reactions for producingthe color change. Also included are any two or more compounds which canundergo a noticeable or measurable physical change, which can bemonitored by appropriate analytical equipment. Such changes includeparticle size, transparency, electric conductivity, magnetism anddissolution. For example, a change in conductivity can be monitored byan electrometer.

A large number of organic and inorganic compounds undergo decompositionwith time and temperature which can be utilized in the instant device.Either the starting material or the decomposition products can bemonitored. For example, ammonium bicarbonate decomposes with time andtemperature to produce ammonia as one of the decomposition productswhich can be monitored with a pH dye. Some typical example of organicand inorganic compounds which undergo thermal decompositions includesodium carbonate, sodium bicarbonate, blowing or foaming agents such asazodicarbonamide, peroxides as benzoyl peroxide, and nitroureas. Thedevices made from these compounds can also be activated by temperature,i.e. by heating the completely assembled device above the decompositiontemperature of the compound. As long as the parent compounds do notmigrate and the decomposed product(s) can be detected with an indicatorwhich would be incorporated in the indicator matrix, they can be used inthe invention device.

The method of activation of the invention device is not limited topressure lamination. The device can also be activated by temperature asdescribed above. If the proper activator is used the device can beactivated by radiation as well. If the activator is microencapsulated,it can be released by applying pressure or temperature. If the activatorcan be decomposed by radiation, the assembled device can be activated byradiation (see "Effect of Radiation on Materials and Components" by J.Kircher and R. Bowman (Ed.). Reinhold Publishing Corp., N.Y. and"Radiation Effects in Materials". Vol. 2, A. Charlesby (Ed.) PergamonPress, N.Y.). For example, diphenyliodonium chloride produces HCl whenirradiated with UV light. Similarly triphenylsulfoniumhexafluoroantimonate produces superacids such as HF and HAsF₆. Theseacids are the activating agents that can diffuse to contact a pH dye.

Photoresist compounds (see, Encycl. Polym. Sci. Eng. Vol 9, 97 (1987)and Amer. Chem. Soc. Symp. Series No. 219 (1983) undergo degradation toprovide low molecular weight materials upon irradiation with high energyradiation such as UV, x-ray, gamma ray and electrons, can also be usedas activators. Positive photoresists which can be utilized in suchmanner include polydimethylketone. halogenated polyethylene,polymethylmethacrylate, poly(olefin sulfone) and poly(hexafluorobutyl)methacrylate. Any compound which does not migrate from the activatormatrix and undergoes chemical reaction with radiation to producecompound(s) which can migrate through the activator matrix and can bedetected by an indicator in the indicator matrix can be used as theactivator in this device.

Certain compounds, especially conjugated polymeric compounds, whenreacted with certain oxidizing, reducing agents or complexing agentsundergo a change in electrical and magnetic properties. The electricalconductivity can be electronic or ionic. For example, when polyacetyleneis exposed to iodine vapor the conductivity of polyacetylene increasesfrom 10⁻⁸ to 10³ S/cm. TTF (tetrathiafulvalene) when reacted with TCNQ(tetracyanoquinodimethane), undergoes several orders increase inconductivity. Similarly, when conductive polyacetylene is exposed toammonia the conductivity decreases back to 10⁻⁸.

Certain compounds when in a reactive state undergo a change intransparency, becoming opaque or more transparent. See for example, U.S.Pat. Nos. 4,345,470 and 4,397,570 both to C. Hot et. al. and assigned toPymah Corp.. Fine powder of most solid compounds are opaque. When suchopaque compounds are dissolved, they become clear or transparent. Alsoas an illustration, opaque benzoic acid in crystalline form can belayered in the indicator matrix positioned on top of a display message,such that the display message is hidden. Triacetin, for example, whichcan dissolve benzoic acid, can be utilized in the activator layer as theactivator and can migrate through the composite matrix layer to contactthe benzoic acid to dissolve it and thus reveal the underlying message.

Certain compounds undergo an observable color change only by a physicalreaction. For example, a number of dyes, when dissolved, undergo a colorchange. Some of the partially polymerized diacetylenes undergo a blue tored color change when exposed to a solvent or its vapor. Such reactionsand activator/indicator systems can also be used in the device.

In principle, there is no limit in the selection of indicators andactivators for use in the devices. Any two or more compounds which canundergo a noticeable or measurable physical or chemical change can beused in the device. The selection of the activators and indicators forthe actual device for a particular perishable will depend on factorsincluding the toxicity and hazardous nature of the chemicals/reactions.

Preferred materials for indicators and activators are those which arenot affected by ambient conditions such as light, air, air pollutants,and moisture and are nontoxic. Water insoluble food additive/ingredientsare particularly preferred as activators. Colors and dyes/pigmentsapproved for dyeing and printing and food colors are preferredindicators.

The following discussion relates to a description of the shelf life of aperishable product, the Arrhenius characteristics of the product decayprocess, and methods for altering the invention device to match theactivation energy and rate constant of color change with the activationenergy and rate constant of product decay of the perishable in thetemperature range of monitoring.

All perishable foods have a measurable shelf-life. Consumeracceptability of any product is mainly judged by its aestheticappearance at the time of sale. The other aspects of quality, such asnutritional, microbiological and toxicological values are of primeimportance, but the consumer is not qualified to make any judgementsregarding them.

The main environmental factor that results in increased loss of qualityand nutrition for most perishables is exposure to increased temperature.The higher the temperature the greater is the loss of the quality. Henceit is extremely important to be able to monitor the shelf life of foods.

The shelf life of most common foods has been reviewed by Labuza [T. P.Labuza, "Application of Chemical Kinetics to Deterioration of Foods", J.Chem. Educ., Vol. 61, page 348 (1984), and T. P. Labuza "Shelf-lifeDating of Foods", Food and Nutrition Press, Westport, Conn. (1982)]. Theshelf life of a large number of foods and beverages has also beenreported in a recent book edited by Charalambous, see "The Shelf-Life ofFoods and Beverages", by G. Charalambous (Ed.), Elsevier, New York,1988.

As previously described above in the discussion of FIG. 1, a plot of thelogarithm of the reaction rate as a function of the reciprocal of(absolute) temperature (1/T) gives a straight line. The slope of eachline is equal to the activation energy divided by the gas constant, "R".A comparatively steeper slope means the reaction is more temperaturedependent; i.e. as the temperature increases, the reaction increases ata faster rate. Also, a lower value for the Y intercept, i.e. value forln k, indicates a faster induction time for either color change orproduct decay.

It is clear from the above discussion that the activation energy andshelf life of the perishable should match with those of thetime-temperature indicator, in the temperature region to be monitored tocompensate for temperature variations during storage. In an ideal case,the kinetic-plot of the indicator should overlap the kinetic-plot of theperishable it is applied to.

FIG. 2 shows Arrhenius plots for some selected perishables. It can bereadily seen that different foods have different activation energies andshelf lives as a function of the particular mode of product decay. Theactivation energy for most, simple hydrolysis reactions is 10-20kcal/mole, lipid oxidation is 15-25 kcal/mole, nonenzymatic browning20-40 kcal/mole and, enzyme and microbial destruction is usually higherthan 40 kcal/mole. For example, the activation energy of deteriorationof beef can vary from 8 to 100 Kcal/mole (see Labuza, supra). The datasummarized by Labuza indicate that perishable foods can have shelf lifeof a few hours to a few years and the associated activation energy canvary from 5 to 100 Kcal/mole. Some perishables have the same activationenergy of decay but different shelf lives and vice versa. For mostperishables the activation energy and the shelf life range from 10 to 70kcal/mole and 6 hours to 5 years respectively. There are thousands ofperishables, each having essentially different kinetics and modes ofdeterioration. Thus the time-temperature indicators for recording theirthermal degradation must be extremely flexible to match the shelf livesand the activation energies of the perishables.

As stated above, in the case of an ideal shelf-life indicator, the plotof the logarithm of time required for color change versus 1/T (Arrheniusplot) of the device should essentially overlap the plot of the logarithmof the shelf-life versus 1/T (Arrhenius plot) of the perishable. In suchcase, the device will change color when the shelf-life of the perishableexpires irrespective of fluctuations in the storage temperature. Inorder to overlap the Arrhenius plot of the device with that of theperishable, the slope of the Arrhenius plot of the device is shifted asshown in schematically in FIGS. 6a and 6b. By changing the slope andshifting the Arrhenius plot of the device, one can overlap the Arrheniusplot of any perishable with that of the device.

For a given temperature, the time required for the color change, and theactivation energy, can be varied by varying the parameters given inTable 4.

Table 4 Major Classes of Parameters for Varying the Time Required forthe Color Change and the Activation Energy of the Tape Device

1. Thickness of the matrices

2. Concentration of the activator

3. Concentration of the indicator

4. Concentration of other additives in the matrices

5. Nature of the activator matrix

6. Nature of the indicator matrix

7. Nature of the barrier matrix

8. Nature of the activator

9. Nature of the indicator

10. Nature of additives in the matrices

11. Nature of the interface between two matrices

12. Mixture of different matrices

13. Mixture of different activators

14. Mixture of additives in the matrices

16. Degree of formation of solid solution between matrix andactivator/additive

The thickness of the indicator, activator and barrier matrices can be asdesired and will for practical purposes be, independently, in the rangeof about 0.001 to 5 mm. Preferably, for food storage monitoring ofperishables, the thickness of each matrix layer is independently in therange of 0.05 to 0.5 mm. Also, preferably the matrices are ofapproximately equal thicknesses. Generally, varying the thickness of amatrix will alter the rate at a particular temperature on the Arrheniusplot of a given device. Larger thicknesses will decrease the given rateof color change production.

The thickness of the barrier matrix can be anywhere from 0.001 to 5 mm.or larger. Preferably, the thickness of the barrier layer in relation tothe indicator and activator layers is about 0.005 to 1 mm.

The concentration of activator in solid solution in the activator matrixis in the region of 0.001 to 0.9 g./cc of matrix and preferably 0.15 to0.5 g./cc. of matrix.

The indicator can either be deposited as a layer on the indicator film1, in a thickness of 0.01 to 5 mm., or can also as the activator, be insolid solution in the indicator matrix, and if so, is present inapproximately the same concentration range as Other additives which canbe utilized in the matrices include those materials which, unless anduntil desired do not react with the matrices, activators, indicators orfilm. It should preferably, form a solid solution at least, with theactivator matrix. It can be an inert compound which just dilutes theconcentration of activator or indicator. It can also aid in forming thesolid solution of the activator.

The additive can also be a reactive compound. For example, if theactivator is an acid, e.g. benzoic acid, a basic compound such asdodecylamine, can be added as an additive in the indicator matrix tochemically control and introduce the induction period. The acid willreact first with the amine until all the amine is reacted, and thenreact with the dye to introduce the color change.

The additive can also be a compound which complexes or interacts withthe activator to slow down, or accelerate its diffusion.

The concentration of the additive in the individual matrix layers canrange from 0.001 to 0.5 g/cc

The nature of the activator, indicator and barrier matrices can bevaried by using independently the polymer films described hereinabove,also including pressure sensitive adhesives.

Adhesives, for example, include the use of synthetic elastomers,acrylates, silicone, synthetic latex and vinyl acetate, asrepresentative examples. The activation energy will in general, for aparticular indicator-activator system, increase from about 10-70kcal/mole proceeding down the above-given matrix series. In general,varying the thickness of a matrix will alter the induction period, i.e.the time required for color change, while varying the nature of thematrix will alter the Eact.

Changing the nature of the indicator or activator in a given device willgenerally alter the Eact of the device as well as the time required forcolor change. Changing only the concentration of the indicator oractivator will generally only affect the induction period for colorchange. The larger the concentration, in general, the faster the rateand lesser time for color change production.

Also, changes in the crystallinity or amorphous nature of the matrix canaffect the Eact. Generally, the more amorphous or less crystalline thematrix , the lower the Eact.

Also, changes in the polarity of the matrix and activator can effect theEact. As a general rule, if the polarity of the activator and the matrixthrough which it is migrating are substantially the same, then the Eactwill be higher. The larger the differences between the respectivepolarities, the lower the Eact in general. For example, see EXAMPLES 2and 3, and examples 13 and 14.

The polarity of the interface between the two matrices affects the Eactfollowing the above rule as in EXAMPLE 3.

The polarity rule as applied to mixtures of different matrices alsoaffects the Eact as seen in EXAMPLE 4.

The use of mixtures of different additives also affects the Eact by thepolarity rule as seen in EXAMPLE 6; as well as the interaction betweenthe matrix and activator/additive combination as seen in EXAMPLES 2 to6.

The degree of formation of solid solution between the matrix andactivator/additive affects the Eact by the general rule that the greaterthe degree of solid solution the lower the Eact for the system. This isseen in EXAMPLE 10.

Although the time required for the color change can be varied by all ofthe factors listed in Table 4, the activation energy of color change canbe mainly varied by factors 5 through 16 and their combinations.

As described above, the activation energy of the device, can be readilyvaried to match that of the perishable. These various methods ofaltering the activation energy will become more readily apparent in theexamples where the methods are illustrated for simplicity by thetwo-layer and three-layer uniform thickness devices.

The color changing tape device of the instant invention has thefollowing combination of major characteristics, benefits and advantagesover those available commercially and those reported in the literature.

1. It can be fashioned into a small and simple device by conventionaltechnology.

2. The device is essentially solid state and water-impermeable.

3. The device can be made inactive until applied to the perishablecontainer.

4. The unactivated device can be made to have an extremely longshelf-life.

5. The device can withstand normal mechanical abuses.

6. Proper activator/indicator combinations are unaffected by humidityand other adverse ambient conditions.

7. The activator/indicator combinations can be selected from a widevariety of nonhazardous chemicals, including food additives and foodingredients.

8. The color change is irreversible.

9. The time required for the color change can be varied by severalorders of magnitude.

10. The activation energy can be varied from 3 to 70 kcal/mole.

11. The degradation kinetics of perishables can be matched with thekinetics of color change of the device.

12. The device can be used for recording and monitoring the thermaldegradation of most perishables.

13. The consumer can read the residual shelf-life from the color of thedevice.

14. The device can be designed to be read by conventionalelectro-optical equipment.

The following examples are illustrative of carrying out the claimedinvention but should not be construed as being limitations on the scopeor spirit of the instant invention.

EXAMPLES IA. Materials Used in the Invention ADHESIVES

The adhesives used in the present invention are listed below in table 5.

                                      TABLE 5                                     __________________________________________________________________________    List of adhesives used as a matrix and their compositions.                    Chemical Name                                                                         Percentage                                                                          Manufacturer &       Thickness                                  of Adhesive                                                                           of solid                                                                            Product #  Solvent medium                                                                          (mil).sup.a                                __________________________________________________________________________    Synthetic                                                                             25    3M         1,1,1-Trichloro-                                                                        1.5                                        Elastomer     Scotch grip 4910 NF                                                                      ethane                                               Synthetic                                                                             25    3M         Oxy-hydrocarbon                                                                         1.5                                        Elastomer     Scotch grip 4914                                                Acrylate                                                                              42    National Starch                                                                          Ethyl acetate, Hep-                                                                     1.5                                                      Duro Tack, 80-1068                                                                       tanes, Toluene                                       Acrylate                                                                              44    3M         Water emulsion                                                                          3.0                                                      Scotch grip 4268                                                Acrylate                                                                              45    Testworth Lab.                                                                           Oxy-hydrocarbon                                                                         2.0                                                      Paralac DF-C119                                                 Silicone                                                                              55    General Electric                                                                         Toluene   3.0                                                      PSA529                                                          Synthetic Latex                                                                       50    United Resin Corp.                                                                       Xylene    3.0                                                      40-0033                                                         Vinyl Acetate                                                                         60    United Resin Corp.                                                                       Water emulsion                                                                          3.0                                                      J8905                                                           __________________________________________________________________________     .sup.a Thickness of the adhesive layer in the device.                    

IB. ACTIVATOR/INDICATOR PAIRS

The following table is a representative list of activator/indicatorcombinations useful in the present invention:

                                      TABLE 6                                     __________________________________________________________________________    List of activator/indicator pairs used in the present invention               Type of Reaction                                                                       Indicator @                                                                          Activator Color change                                                                            Comments                                  __________________________________________________________________________    Dissolution                                                                            pp4BCMU                                                                              Triacetin Blue-red  Unaffected by                                       "     Tributaryn                                                                               "        moisture.                                           "     Linoleic acid                                                                            "                                                            "     Heptanoic acid                                                                           "                                                  pH Change                                                                              BPB-Na salt                                                                          Adipic acid                                                                             Blue-green-yellow                                                                       Food                                                "     Benzoic acid                                                                             "        additives                                           "     Citric acid                                                                              "                                                            "     Vitamin-C  "                                                           PTM    Citric acid                                                                             Colorless-red                                                 "     Vitamin-C  "                                                  Oxidation                                                                              LeucoMG                                                                              Ammoniumper                                                                             Colorless-green                                                     sulfate                                                       Reduction                                                                              MG     Sodiumsulfite                                                                           Green-Colorless                                     Decomposition                                                                          BPB    Sodiumcarbonate                                                                         Yellow-green-blue                                             "     Sodiumbicarbonate                                                                        "                                                  __________________________________________________________________________     Notes @:                                                                      pp4BCMU = Partially polymerized 4BCMU                                         BPB-Na salt = Bromophenolblue sodium salt                                     BPB = Bromophenolblue (water insoluble)                                       PTM = pentamethoxytriphenylmethane                                            LeucoMG = Leucomalachite green                                                MG = Malachite green                                                     

METHODS

The following methods were used for preparation of tapes and devices:

Method 1. General Method of Preparinq Solutions of Indicators andActivators in a Pressure Sensitive Adhesive Matrix

A known weight, e.g. 0.2 g of an indicator or 1.0 g of an activator, aknown weight (e.g. 5 g) of a solvent, (if used for the indicator, andrequired for the activator to be dissolved) and a known weight (e.g. 4g) of a pressure sensitive adhesive matrix (see above table 5) wereplaced in a 25 ml polypropylene tube and dissolved by spinning themixture in a Rotavapor Model-R110 (Brinkman Instrument Inc., Westbury,N.Y.) for 5 minutes. The resulting solid solution was used for coating.

Method 2. General Method of Preparing Solutions of Indicators andActivators in an Ink Medium (Layers)

A known weight, e.g. 0.1 g of an indicator or 1.0 g of an activator, aknown weight (e.g. 9.0 g) of about 4% solution of ink matrix (e.g.cellulose nitrate) in a suitable solvent (e.g. ethylacetate) were placedin a 25 ml polypropylene tube and dissolved by spinning the mixture in aRotavapor Model-R110 (Brinkman Instrument Inc., Westbury, N.Y.) for 5minutes. The resulting solution was used for coating.

Method 3. General Method of Coating for Adhesive Medium

A 5 mil thick, 8×18 inch polyester sheet (Mylar, DuPont) was laid flaton a x-y recorder (disconnected from a Electron Spin ResonanceSpectrophotometer, Model E-4, Varian, Palo Alto, Calif.) and held inplace by an inbuilt suction of the recorder. A Bird type wet filmapplicator of cut depth 0.0015 or 0.006 inch (obtained from Paul GardnerCompany, Inc., Pompano Beach, Fla.) was placed at one end of thepolyester sheet against the arm of the recorder. 10 g of the indicatoror activator mixture prepared according to the procedure described inMethods 1 or 2 was poured in a straight line in front of the wet filmapplicator and the applicator was moved across the face of the film at aconstant speed of 4" per minute by setting the scanning speed of therecorder. The resulting film was allowed to dry for about 24 hours atroom temperature. This constitutes the indicator or activator tape.

Method 4. General Method for Device Activation

The device was activated (assembled) by laminating the indicator tapeand activator tape so that the activator matrix faces the indicatormatrix. At least one of the matrices is a pressure sensitive adhesive.Gentle pressure using a hand roller or finger pressure was applied toobtain uniform bonding between the indicator and activator media.

Method 5. General Method of Preparation of Stationary 4BCMU Indicatortape

A known weight (e.g. 1 g) of 4BCMU [a diacetylene,R--C.tbd.C--.tbd.C--R, where R is (CH₂)₄ OCONHCH₂ COO(CH₂)₃ CH₃ ]synthesized according to procedure of Patel (Polymer Preprint, 19(2), pp154-159, (1978) and U.S. Pat. No. 4,452,995 assigned to Allied ChemicalCorp.), 5 g of chloroform and 4 g of a polymeric resin (e.g. an adhesiveor ink matrix) were placed in a plastic tube and dissolved by spinningthe mixture in a Rotavapor for 5 minutes according to procedure describein Method 1.

The indicator tape was prepared by coating the above solution accordingto the procedure described in Method 3. The tape was allowed to dry fora day. The coating of 4BCMU was then exposed to a short wavelength (254nm) UV lamp for partial polymerization of 4BCMU, until the colorlesscoating turned moderately blue. This partially polymerized 4BCMU isreferred to hereinafter as "pp4BCMU".

Many partially polymerized diacetylenes including 4BCMU undergo a blueto red color change when contacted with a solvent which dissolves theunreacted monomer. 4BCMU was experimentally tested to determine whetheran indicator/activator system which undergoes a physical reaction can beused for preparation of the device.

Method 6. General Method of Preparation of Activator Tape for 4BCMU

A known weight (e.g. 1 g) of an activator (e.g. triacetin) which hasability to dissolve 4BCMU monomer and 9 g of polymeric medium (e.g. apressure sensitive adhesive matrix layer) were mixed according to thegeneral procedure describe in Method 1.

The activator tape was prepared by coating the above solution accordingto the procedure described in Method 3. The tape was allowed to dry atleast for a day.

The stationary device utilized for Examples 2 to 8 was a two-layerdevice, in which the activator tape was made by Method 6, the indicatortape by Method 5, and the two layers laminated together according toMethod 4.

The effects of various parameters on time required for the color changeand the activation energy of the device were experimentally studied.Because of the voluminous data, tables of time required for the colorchange at different temperatures are not presented. Instead, the samedata are presented in form of plots of logarithm of time required forthe color change versus reciprocal of temperature, the Arrhenius plots.The activation energy was calculated from slopes of the Arrhenius plots.The plots are illustrated as FIGS. 7-12.

EXAMPLE 1 Control Devices

The indicator, pp4BCMU was incorporated into a adhesive listed in table5. Corresponding activator tapes were prepared from the same adhesiveswithout using any kind of activators. Both the tapes were thoroughlydried. The devices were activated with applying the activator tapes overthe indicator tapes according to method 4. None of the device changecolor after some months at room temperature indicating that the colorchange in the examples 2-8 is due to the activators used.

EXAMPLE 2 Effect of the Nature of the Matrix on the Activation EnergyWhen the Activator and Indicator Matrices are the Same Material

The indicator, pp4BCMU and the activator, triacetin were incorporatedinto the same matrix materials. Three different matrix materials wereused. The Arrhenius plots for these systems are shown in FIG. 7. Theeffect of variation of matrix on the activation energy when theindicator and the activator are in the same matrix material arepresented in the table below. As can be seen from table 7, theactivation energy can be varied from 31 to 62 kcal/mole by changing thenature of the matrix material.

                                      TABLE 7                                     __________________________________________________________________________    Variation in activation energy when indicator and                             activator matrices are the same materials. Concentrations of                  activators and indicators in the matrix are given in the parentheses.         SYSTEM:                                                                       Indicator Tape: Indicator: pp4BCMU, Concn.: Varied; Matrix: Varied            Activator Tape: Activator: TA, Concn.: Varied; Matrix: Varied                                              Activation                                       Indicator System                                                                              Activator System                                                                           Energy                                                                              Plot #                                     Indicator                                                                              Matrix Activator                                                                           Matrix (kcal/mole)                                                                         FIG. 7                                     __________________________________________________________________________    pp4BCMU (17%)                                                                          Silicone                                                                             TA (17%)                                                                            Silicone                                                                             62    1                                          pp4BCMU (30%)                                                                          Acrylate/TW                                                                          TA (22%)                                                                            Acrylate/TW                                                                          34    2                                          pp4BCMU (8%)                                                                           Elastomer                                                                            TA (31%)                                                                            Elastomer                                                                            31    3                                          __________________________________________________________________________     Notes:                                                                        See table 5 for the manufacturers of the adhesives an their properties.       Unless specified concentration of catalyst for the silicone resin was 3%.     TA = Triacetin, TW = Testworth Lab. and pp4BCMU = Partially polymerized       4BCMU                                                                    

EXAMPLE 3 Effect of the Nature of the Matrix on the Activation EnergyWhen Activator and Indicator Matrices are Different

The indicator, pp4BCMU was incorporated into a synthetic elastomer andthe activator, triacetin was incorporated in several other matrices. TheArrhenius plots for these systems are shown in FIG. 8. The effect ofvariation of matrix on the activation energy when the indicator and theactivator are in different matrices are presented in table 8. As can beseen, the activation energy can be varied from 20 to 50 kcal/mole.

                                      TABLE 8                                     __________________________________________________________________________    Variation in the activation energy when indicator and                         activator matrices are different materials. Concentrations of                 activators and indicators in a particular matrix are given in the             parentheses.                                                                  SYSTEM:                                                                       Indicator Tape: Indicator: pp4BCMU, Concn.: 8%; Matrix: Elastomer             Activator Tape: Activator: TA, Concn.: Varied; Matrix: Varied                                              Activation                                       Indicator System                                                                             Activator System                                                                            Energy                                                                              Plot # in                                  Indicator                                                                              Matrix                                                                              Activator                                                                           Matrix  (kcal/mole)                                                                         FIG. 8                                     __________________________________________________________________________    pp4BCMU (8%)                                                                           Elastomer                                                                           TA (31%)                                                                            Elastomer                                                                             31    1                                          pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Acrylate/TW                                                                           50    2                                          pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Acrylate/NS                                                                           45    3                                          pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone                                                                              44    4                                                               (0.6% Catalyst)                                          pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Vinylacetate                                                                          39    NOT SHOWN                                  pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone                                                                              20    "                                                               (3% catalyst)                                            __________________________________________________________________________     Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless specified concentration of catalyst for the silicone resin was 3%.     TA = Triacetin, TW = Testworth Lab., NS = National Starch, and pp4BCMU =      Partially polymerized 4BCMU                                              

EXAMPLE 4 Effect of Matrix Mixtures on the Activation Energy

The indicator, pp4BCMU was incorporated in a synthetic elastomer and theactivator, triacetin was incorporated into mixtures of four differentmatrix materials. The Arrhenius plots for these systems are shown inFIG. 9. The effect of matrix 0 mixtures on the activation energy ispresented in table 9. It can be seen that the activation energy can bevaried from 20 to 50 kcal/mole by selecting and mixing appropriateamounts of the matrix mixtures for the activator.

                                      TABLE 9                                     __________________________________________________________________________    Effect of matrix mixtures on the activation energy. Concentrations            of activators and indicators in the matrix materials are given in the         parentheses.                                                                  SYSTEM:                                                                       Indicator Tape: Indicator: pp4BCMU, Concn.: 8%; Matrix: Elastomer             Activator Tape: Activator: TA, Concn.: Varied; Matrix: Varied                                                Activation                                     Indicator System                                                                             Activator System                                                                              Energy                                                                              Plot # in                                Indicator                                                                              Matrix                                                                              Activator                                                                           Matrix    (kcal/mole)                                                                         FIG. 9                                   __________________________________________________________________________    pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Acrylate/TW                                                                             50    1                                        pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Elastomer +                                                                             42    2                                                             Acrylate/TW (7:3)                                        pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Elastomer +                                                                             40    NOT SHOWN                                                     Acrylate/TW (3:7)                                        pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone  20    4                                                             (3% catalyst)                                            pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone +                                                                              23    5                                                             Elastomer (3:7)                                          pp4BCMU (8%)                                                                           Elastomer                                                                           TA (31%)                                                                            Elastomer 31    NOT SHOWN                                __________________________________________________________________________     Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless specified concentration of catalyst for the silicone resin was 3%.     TA = Triacetin, TW = Testworth Lab., and pp4BCMU = Partially polymerized      4BCMU                                                                    

EXAMPLE 5 Effect of Different Activators on the Activation Energy

The indicator, pp4BCMU was incorporated into a synthetic elastomer anddifferent activators, including triacetin and linoleic acid wereincorporated into silicone and elastomer matrices. The Arrhenius plotsfor these systems are shown in FIG. 10. The effect of differentactivators on the activation energy is presented in table 10. It is seenthat the activation energy can be varied from 68 to 20 kcal/mole byselecting a proper activator.

                                      TABLE 10                                    __________________________________________________________________________    Effect of variation of activator on the activation energy.                    Concentrations                                                                of activators and indicators in the matrix are given in the parentheses.      SYSTEM:                                                                       Indicator Tape: Indicator: pp4BCMU, Concn.: 8%; Matrix: Elastomer             Activator Tape: Activator: Varied, Concn.: Varied; Matrix: Varied                                        Activation                                         Indicator System                                                                             Activator System                                                                          Energy                                                                              Plot # in                                    Indicator                                                                              Matrix                                                                              Activator                                                                           Matrix                                                                              (kcal/mole)                                                                         FIG. 10                                      __________________________________________________________________________    pp4BCMU (8%)                                                                           Elastomer                                                                           LA (28%)                                                                            Elastomer                                                                           33    1                                            pp4BCMU (8%)                                                                           Elastomer                                                                           TA (31%)                                                                            Elastomer                                                                           31    2                                            pp4BCMU (8%)                                                                           Elastomer                                                                           LA (28%)                                                                            Silicone                                                                            68    3                                            pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone                                                                            20    4                                            __________________________________________________________________________     Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless specified concentration of catalyst for the silicone resin was 3%.     TA = Triacetin, LA = Linoleic acid, and pp4BCMU = Partially polymerized       4BCMU                                                                    

EXAMPLE 6 Effect of Activator Mixtures on the Activation Energy

The indicator, pp4BCMU was incorporated into a synthetic elastomer and amixture of two activators, triacetin and linoleic acid, was incorporatedin silicone matrix. The Arrhenius plots for some of these systems areshown in FIG. 11. The effect of the mixture of activators on activationenergy is presented in table 11. As can be seen from table 11, theactivation energy can be varied from 20 to 68 kcal/mole by usingmixtures of activators.

                                      TABLE 11                                    __________________________________________________________________________    Effect of activator mixtures on the activation energy. Concentrations         of activators and indicators in the matrix are given in the parentheses.      SYSTEM:                                                                       Indicator Tape: Indicator: pp4BCMU, Concn.: 8%; Matrix: Elastomer             Activator Tape: Activator: Varied, Concn.: Varied; Matrix: Silicone                                          Activation                                     Indicator System                                                                             Activator System                                                                              Energy                                                                              Plot # in                                Indicator                                                                              Matrix                                                                              Activator                                                                              Matrix (kcal/mole)                                                                         FIG. 11                                  __________________________________________________________________________    pp4BCMU (8%)                                                                           Elastomer                                                                           LA (28%) Silicone                                                                             68    1                                                                (3% catalyst)                                         pp4BCMU (8%)                                                                           Elastomer                                                                           TA + LA (22%)                                                                          Silicone                                                                             34    2                                                       (1:1)    (3% catalyst)                                         pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%) Silicone                                                                             20    3                                                                (3% catalyst)                                         __________________________________________________________________________     Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless specified, the concentration of catalyst for the silicone resin wa     3%.                                                                           TA = Triacetin, LA = Linoleic acid, and pp4BCMU = Partially polymerized       4BCMU                                                                    

EXAMPLE 7 Effect of Adhesive Tack on the Activation Energy

The tackiness (adhesive ability, formation of adhesive bond with asubstrate) of some adhesives can be varied by adding a tackifier or acatalyst. The adhesive ability of silicone adhesives can be decreased toalmost nonadhesive nature by adding certain proprietary catalysts whichcrosslink the adhesive. The catalyst for the silicone adhesive usedherein was also supplied by the manufacturer. In order to study theeffect of catalyst (which decreases the tackiness) on the activationenergy, triacetin was incorporated in silicone adhesive containingdifferent concentrations of the catalyst. The indicator, pp4BCMU wasincorporated into a synthetic elastomer. The Arrhenius plots for thesesystems are shown in FIG. 12. The effect of concentration of thecatalyst on the activation energy is presented in table 12. As can beseen, the activation energy can be varied from 44 to 20 kcal/mole byvarying the tackiness (concentration of the catalyst from 0.6 to 3%) ofthe matrix.

                                      TABLE 12                                    __________________________________________________________________________    Effect of variation of adhesive tack on the activation energy.                Concentrations                                                                of activators and indicators in the matrix are given in the parentheses.      SYSTEM:                                                                       Indicator Tape: Indicator: pp4BCMU, Concn.: 8%; Matrix: Elastomer             Activator Tape: Activator: Triacetin, Concn.: Varied; Matrix: Silicone                                     Activation                                       Indicator System                                                                             Activator System                                                                            Energy                                                                              Plot # in                                  Indicator                                                                              Matrix                                                                              Activator                                                                           Matrix  (kcal/mole)                                                                         FIG. 12                                    __________________________________________________________________________    pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone                                                                              44    1                                                               (0.6% Catalyst)                                          pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone                                                                              20    2                                                               (3% catalyst)                                            __________________________________________________________________________     Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless specified concentration of catalyst for the silicone resin was 3%.     TA = Triacetin, and pp4BCMU = Partially polymerized 4BCMU                

SUMMARY OF THE ACTIVATION ENERGY RESULTS

Table 13 summaries the effects of different variables on the activationenergy. As is seen, by varying the nature of activator and the matrix,one can vary the activation energy from 20 to 68 kcal/mole. Thoughselected variables were only studied over a limited range, it is evidentthat the device is extremely flexible. It is possible, utilizing theabove methodology, to vary the time required for the color change, andthe activation energy, for most TTM systems reported in the literature.For the pp4BCMU system, we have demonstrated that the activation energycan at least be varied from 20 to 68 kcal/mole. By selecting and varyingthe nature of the other parameters listed in table 4, the activationenergy can be varied over very wide range, e.g. from 1 to 200 kcal/mole.

                                      TABLE 13                                    __________________________________________________________________________    Summary of the effect of variables on the activation energy of the 4BCMU      device.                                                                       Concentrations of initiators and indicators in a particular matrix are        given in parentheses.                                                         SYSTEM:                                                                       Indicator Tape: Indicator: pp4BCMU, Concn.: Varied; Matrix: Varied            Activator Tape: Activator: Varied, Concn.: Varied; Matrix: Varied                                            Eact                                                                              Perishable having the                      Indicator System                                                                             Activator System                                                                              (kcal/                                                                            same Eact, see page #                      Indicator                                                                              Matrix                                                                              Activator                                                                           Matrix    mole                                                                              in book by Labuza                          __________________________________________________________________________    pp4BCMU (17%)                                                                          Elastomer                                                                           LA (28%)                                                                            Silicone  68  Asparagus p 334                            pp4BCMU (17%)                                                                          Silicone                                                                            TA (17%)                                                                            Silicone  62                                             pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Acrylate/TW                                                                             50  Snap bean p 334                            pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Acrylate/NS                                                                             45  Raspberries p 337                          pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone  44  Strawberries p 337                                              (0.6% catalyst)                                          pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Elastomer +                                                                             42  Asparagus p 334                                                 Acrylate/TW (7:3)                                        pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Elastomer +                                                                             40  Peas p 335                                                      Acrylate/TW (3:7)                                        pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Vinylacetate                                                                            39  Wheat p 90                                 pp4BCMU (8%)                                                                           Elastomer                                                                           TA + LA                                                                             Silicone  34  Broccoli p 335                                            (1:1)                                                          pp4BCMU (30%)                                                                          Acrylate                                                                            TA (22%)                                                                            Acrylate/TW                                                                             34  Broccoli p 335                             pp4BCMU (8%)                                                                           Elastomer                                                                           LA (28%)                                                                            Elastomer 33  Lima beans p 334                           pp4BCMU (8%)                                                                           Silicone                                                                            TA (31%)                                                                            Elastomer 32  Sweet corn p 253                           pp4BCMU (8%)                                                                           Elastomer                                                                           TA (31%)                                                                            Elastomer 31  Chicken p 155                              pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone +                                                                              23  Fish-Halibut p 185                                              Elastomer (3:7)                                          pp4BCMU (8%)                                                                           Elastomer                                                                           TA (22%)                                                                            Silicone  20  Milk p 201                                 __________________________________________________________________________     Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless specified concentration of catalyst for the silicone resin was 3%.     Ea = Activation energy of the device, TA = Triacetin, LA = Linoleic acid,     TW = Testworth Lab., NS = National Starch, and pp4BCMU = Partially            polymerized 4BCMU.                                                            Notes for the last column:                                                    The perishables reported in this column are based on the activation energ     reported in the book by Labuza. Page numbers are given for reference wher     the same data is listed after the perishable. Once the activation energy      of the perishable is established, the shelf life of the perishable can be     matched by varying the time required for the color change of the device       using the techniques described in the following examples.                

EXAMPLE 8 Variation in Time Required for the Color Change

During the activation energy study reported above, the time required forthe color change was recorded. The time required for the initiation ofthe color change can be varied by several orders of magnitude by varyingthe parameters listed in table 4. A typical example is given in table14, where the time required for the color change has been varied by overthree orders of magnitude by varying the activator. Thus it is possibleto vary the time required for the color change by several orders ofmagnitude.

                  TABLE 14                                                        ______________________________________                                        Time required for the color change for pp4BCMU system at 7° C.         SYSTEM:                                                                       Indicator Tape: Indicator: pp4BCMU, Concn.: 8%;                               Matrix: Elastomer                                                             Activator Tape: Activator: Varied, Concn.: Varied;                            Matrix: Varied.                                                                                           Color Initiation                                  Indicator System                                                                           Activator System                                                                             Time (in minutes                                  Indicator                                                                             Matrix   Activator Matrix and hours)                                  ______________________________________                                        pp4BCMU Elasto-  LA (22%)  Silicone                                                                             10,200 min                                  (8%)    mer                       (170 hrs)                                   pp4BCMU Elasto-  TB (31%)  Elasto-                                                                                 10 min                                   (8%)    mer                mer    (0.17 hr)                                   ______________________________________                                         Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless specified concentration of catalyst for the silicone resin was 3%.     TB = Tributarin, LA = Linoleic acid, and pp4BCMU = Partially polymerized      4BCMU                                                                    

EXAMPLE 9 Use of Acids as Activators and pH Dyes as Indicators

A wide range of dyes which are sensitive to acids and bases arecommercially available. One of the water insoluble dye(pentamethoxytriphenylmethane, PTM) undergoes a colorless to red colorchange when exposed to water insoluble acids such as benzoic acid. Thistype of dye/acid combination can provide a tape device which can beunaffected by moisture. The other dye, bromophenol blue sodium salt(BPB-Na) undergoes a series of color change, blue to green-blue to greento yellow-green to yellow to orange to red when exposed to acids such ascitric acid and vitamin-C (L-ascorbic acid). This type of dyes canprovide desirable visual colors e.g. green to yellow to red. These dyeswere incorporated into different adhesives and used as the indicatortape. Organic acids, including citric acid, vitamin-C, benzoic acid,heptanoic, and adipic acids were incorporated into different adhesivesand coated on Mylar film to produce the activator tape. The devices wereactivated by laminating the activator tape over the indicator tape.

An indicator tape was prepared by mixing 0.8 g of2,2',4,4',4"-pentamethoxytriphenylmethanol (PTM) and 8 g of acrylicadhesive (Scotch Grip 4268, 3M Company) according to the proceduredescribed in Method 3. An activator tape was prepared by mixing 2.0 g ofcitric acid and 9.8 g of vinyl acetate adhesive (J8905, United Resin,Inc.) according to the procedure described in Method 3. The devices wereprepared (activated) by laminating the activator tape on to theindicator tape according to the procedure described in Method 4. Severalsuch devices were annealed at different temperatures and the timerequired for initiation of the color change (colorless to red) wasnoted. The time required for the color change was 44, 38, 15, and 8minutes at 60°, 70°, 80° and 90° C. The activation Energy determinedfrom the Arrhenius plot was 13 kcal/mole. The results for the othersystems, i.e., adipic acid, benzoic acid, and vitamin-C as activatorsand pentamethoxytrimethoxy methanol and bromophenol blue --sodium saltas indicators using different adhesives as the matrix, are summarized intable 15.

                                      TABLE 15                                    __________________________________________________________________________    Activation energy of pH sensitive systems having citric acid and sodium       carbonate as an acti-                                                         vator combination. Concentration of activators and indicators are             presented in parentheses:                                                     SYSTEM:                                                                       Indicator Tape: Indicator: Varied, Concn.: Varied; Matrix: Varied             Activator Tape: Activator: Varied, Concn.: Varied; Matrix: Varied                                                    Activation                             Indicator System       Activator System                                                                              Energy                                 Indicator      Matrix  Activator                                                                              Matrix (kcal/mole)                            __________________________________________________________________________    BPB--Na (2%)   Syn. Latex                                                                            Citric acid (3%)                                                                       Vinylacetate                                                                         20                                     BPB--Na (2%) + SC (0.5%)                                                                      "       "        "     24                                     BPB--Na (2%)    "      Citric acid (16%)                                                                      Elastomer                                                                            20                                     BPB--Na (2%) + SC (0.5%)                                                                      "       "        "     22                                     PTM (2%)       Elastomer                                                                             Citric acid (3%)                                                                        "     15                                     PTM (2%)       Acrylate                                                                               "       Vinylacetate                                                                         13                                     BPB (3%)       Vinylacetate                                                                          SC (4%)   "     10                                     BPB (3%)       PVC/Acrylate                                                                          SC (5%)  Syn Latex                                                                            20                                     __________________________________________________________________________     Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless specified concentration of catalyst for the silicone resin was 3%.     BPB--Na = Bromophenol blue sodium salt BPB =  Bromophenol blue, PTM =         Pentamethoxytriphenylmethane, and SC = Sodium carbonate.                 

Comparing the activation energy results summarized in table 13, wherethe activators of relatively low polarity compounds were used, withthose reported in table 15, where the activators have higher polarity,it is seen that for the same adhesive matrices, the activation energy islower when the polarity of the activator is increased. This effectbecomes more apparent in examples 13 and 14, where highly polar (highlyionizable) inorganic compounds are used as the activators.

EXAMPLE 10 Induction Period

In addition to the parameters described in Table 4, there are severalother parameters such as incorporation of activator-reactive additivesin the indicator matrix that can also increase the induction period. Forexample, citric acid reacts with sodium carbonate, a simple acid/basereaction. The reaction between sodium carbonate and citric acid can notbe seen because it is not associated with color change. If sodiumcarbonate is also incorporated in to the indicator matrix, citric aciddiffusing into the indicator matrix will first react with (be consumedby) sodium carbonate. Once all sodium carbonate is consumed, citric acidthen will react with the dye to introduce color change. Thus, it willrequire a longer time to see the color change. The induction period willdepend upon the concentration of the reactive additive. The inductionperiod will increase with increase in concentration of the additive.Thus the induction period can be increased without changing theactivation energy.

We have observed that if the concentration of citric acid issignificantly high, i.e., more than 50%, it will crystallize out of thematrix and will not migrate to the indicator layer to introduce a colorchange.

Two indicator tapes were prepared from synthetic latex (40-0033, UnitedResin) one containing 2% of bromophenol blue and other containing 2% ofbromophenol blue plus 0.5% sodium carbonate according to the proceduredescribed in Method 3. An activator tape was prepared from vinyl acetateadhesive (J8905, United Resin, Inc.) containing 2% citric acid accordingto the procedure described in Method 3. The devices were prepared(activated) by laminating the activator tape on to the indicator tapesaccording to procedure described in Method 4. The time required forinitiation of blue to yellow color change was noted. The devicecontaining bromophenol blue required 480 minutes while that containingbromophenol blue plus sodium carbonate required 840 minutes for the blueto yellow color change. The results for the other systems are summarizedin table 16.

                                      TABLE 16                                    __________________________________________________________________________    Effect of thickness and additives on time required for color change at        90° C.                                                                 Concentration of activator and indicator is presented in parentheses.         SYSTEM:                                                                       Indicator Tape: Indicator: Varied, Concn.: Varied; Matrix: Varied             Activator Tape: Activator: Varied, Concn.: Varied; Matrix: Varied             Indicator System     Activator System                                                                              Time for color                           Indicator      Matrix                                                                              Activator                                                                              Matrix Change (min)                             __________________________________________________________________________    PTM (2%)       Elastomer                                                                           Citric acid (16%)                                                                      Elastomer                                                                             2                                       PTM (2%)       Acrylate                                                                            Citric acid (2%)                                                                       Vinylacetate                                                                          8                                       BPB--Na (2%)   Syn Latex                                                                            "        "     480                                      BPB--Na (2%) + SC (0.5%)                                                                      "     "        "     840                                      BPB--Na (2%)    "    Citric acid (16%)                                                                      Elastomer                                                                            860                                      BPB--Na (2%) + SC (0.5%)                                                                      "     "        "     1800                                     __________________________________________________________________________     Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless specified concentration of catalyst for the silicone resin was 3%.     PTM = Pentamethoxytriphenylmethane, BPB--Na = Bromophenol blue sodium         salt, SC = Sodium carbonate                                              

EXAMPLE 11 Use of an Oxidant as Activator and Redox Dye as Indicator

An indicator tape was prepared from elastomeric adhesive (4910 3MCompany) containing 7% of leucomalachite green as a reduced dyeaccording to the procedure described in Method 3. An activator tape wasprepared from vinyl acetate adhesive (J8905, United Resin, Inc.)containing 4% ammonium persulfate as an oxidant according to theprocedure described in Method 3. The device was prepared (activated) bylaminating the activator tape onto the indicator tape according to theprocedure described in Method 4. The assembled tape was cut into severalsmaller devices which were annealed in the temperature range of 35 to 75degrees centigrade and the time required for initiation of color change(colorless to green) was noted. For example, one device, annealed at 35+C. required 66 minutes, and another device annealed at 75° C. required 4minutes. The activation Energy determined from the Arrhenius plot was 24kcal/mole. The results are summarized in table 17.

                  TABLE 17                                                        ______________________________________                                        Activation energy of oxidizing and reducing systems. Concen-                  tration of activator and indicator is presented in parentheses.               SYSTEM:                                                                       Indicator Tape: Indicator: Varied, Concn.: Varied; Matrix: Varied             Activator Tape: Activator: Varied, Concn.: Varied;                            Matrix: Varied                                                                              Activator System                                                                           Activation                                         Indicator System                                                                              Acti-              Energy                                     Indicator Matrix    vator   Matrix   (kcal/mole)                              ______________________________________                                        LeucoMG (7%)                                                                            Elastomer AP      Vinylacetate                                                                           24                                                           (4%)                                                      MG (0.5)  "         SS      "        24                                                           (2%)                                                      ______________________________________                                         Notes:                                                                        See table 5 for the manufacturers of the adhesives and their properties.      Unless otherwise specified, the concentration of catalyst for the silicon     resin was 3%.                                                                 LeucoMG = Leuco malachite green, MG = Malachite green, APS = Ammonium         persulfate, and SS = Sodium sulfite.                                     

EXAMPLE 12 A Reducing agent as an Activator and a Redox Dye as anIndicator

An indicator tape was prepared from an elastomeric adhesive (4910 3MCompany) containing 0.5% of malachite green as an oxidized dye accordingto the procedure described in Method 3. An activator tape was preparedfrom vinyl acetate adhesive (J8905, United Resin, Inc.) containing 2% ofsodium sulfide as a reducing agent according to the procedure describedin Method 3. The device was prepared (activated) by laminating theactivator tape on to the indicator tape according to procedure describedin Method 4. The assembled tape was cut into several smaller devices andwere annealed in a temperature range of 70-90 degrees centigrade, andthe time required for initiation of color change (green to colorless)was noted. For example, one device, annealed at 70° C. required 165hours, while another device, annealed at 90° C. required 22 hours. Theactivation Energy determined from the Arrhenius plot was 24 kcal/mole.The results are summarized above in Table 17.

EXAMPLE 13 Cation as an Activator

An indicator tape was prepared by mixing 100 mg of 2,2'-bipyridyl and 10g of synthetic elastomer (4910, 3M Company) according to the proceduredescribed in Method 3. An activator tape was prepared by mixing 500 mgof ferrous sulfate and 10 g of vinyl acetate (United Resin J8905)according to the procedure described in Method 3. The device wasprepared (activated) by laminating the activator tape onto the indicatortape according to procedure described in Method 4. Two devices, thusmade, were annealed at 25°, 50°, and 74° C. and the time required forinitiation of color change (colorless to red) was 20, 13 and 10 minutes,respectively. The Eact of the device was 2.9 kcal/mole.

The activation energy of this system is so low that it can be usedessentially for monitoring time. The effect of temperature is almostnegligible.

EXAMPLE 14 Anion as an Activator

An indicator tape was prepared by mixing 200 mg of ferric chloride, 1 gwater and 10 g of vinyl acetate (United Resin J8905) according to theprocedure described in Method 3. An activator tape was prepared bymixing 500 mg of sodium thiocyanate, 1 g water and 10 g of vinyl acetate(United Resin J8905) according to the procedure described in Method 3.The device was prepared (activated) by laminating the activator tape onto the indicator tape according to procedure described in Method 4. Twodevices, made thus, were annealed at 25°, 50°, and 70° C. and the timerequired for initiation of color change (brown to red) was 30, 20, and15 minutes, respectively. The Eact of the device was 3.1 kcal/mole. Theactivation energy of this system is so low that it can be usedessentially for monitoring time. The effect of temperature is almostnegligible.

It can be seen from results summarized in tables 13 and 15, and examples13 and 14 that the Eact can be decreased by increasing the difference inpolarity (or ionization) of the activator and the matrix. For example,when a nonpolar elastomer is used as a matrix for activator, the Eact isusually higher than 30 kcal/mole for nonionizable/nonpolar organicactivator (table 13), the Eact is higher than 15 kcal/mole forpolar/ionizable organic compounds such as citric acid (table 15), andthe Eact is less than 10 kacl/mole for ionic activator (examples 13 and14).

EXAMPLE 15 Change in Fluorescence

An indicator tape was prepared by mixing 200 mg of 8-hydroxyquinolineand 10 g of synthetic elastomer (Scotch-Grip 4910, 3M) using theprocedure described in Method 3. This coating was done on polyethylenesubstrates. An activator tape was prepared by mixing 500 mg of magnesiumchloride, 1 g water and 9 g of vinyl acetate (United Resin J8905) usingthe procedure described in Method 3. The device was prepared (activated)by laminating the activator tape on to the indicator tape according toprocedure described in Method 4. The device was kept at 80° C. for 2 hrsand checked for fluorescence under short wavelength UV at 254 nm. Thedevice, which did not fluoresce at the time of activation, showed abluish fluorescence under UV light after the annealing.

EXAMPLE 16 Message Device

An activator tape was prepared by coating a mixture of 0.5 g citric acidand 10 g synthetic Elastomer (Scotch Grip 4914, 3M Company) as describedin Method 3. An indicator tape was prepared by writing the followingmessage with an ink (mixture of pentamethoxytriphenyl methanol andpolyvinylchloride in tetrahydrofuran) on a polyester sheet:

"IF RED, DO NOT USE".

The device was prepared (activated) by laminating the activator tapeonto the indicator tape according to procedure described in Method 4.The colorless message became red in color within one hour at roomtemperature.

EXAMPLE 17 Production of Activator by Thermal Decomposition in theAssembled Device

An indicator tape was prepared by mixing 100 mg of bromophenol blue and10 g of synthetic elastomer (4910, 3M Company) according to theprocedure described in Method 3. An activator tape was prepared bymixing 1 g of ammonium carbonate and 10 g of vinyl acetate (United ResinJ8905) according to the procedure described in Method 3. The device wasprepared (activated) by laminating the activator tape on to theindicator tape according to procedure described in Method 4. Theassembled tape was cut into several smaller devices and were annealed inthe temperature range 50° to 90° C., and the time required forinitiation of color change was noted. The device annealed at 50° C.turned green after 20 minutes; the one annealed at 70° C. in 7 min.; theone at 80° C. in 5 min.; the one at 90° C. in 3 min.; and the one atroom temperature after 1 hour.

EXAMPLE 18 Production of Activator by UV Irradiation of Assembled Device

An indicator tape was prepared by mixing 1 g of triphenyl sulfoniumhexafluoroantimonate and 10 g of acrylic adhesive (Durotech 80-1068,National Starch) using the procedure described in Method 3. This coatingwas done on 4 mil polyethylene film. An activator tape was prepared bymixing 100 mg of pentamethoxytriphenyl methanol and 10 g of acrylic(Duro-Tak 80-1068) using the procedure described in Method 3. The devicewas assembled by laminating the activator tape on to the indicator tapeaccording to procedure described in Method 4. The device did not changecolor when protected from UV light. The laminated device was activatedby exposing to a short wavelength UV light through the polyethylenesubstrate for a minute. Upon UV irradiation, the activator, triphenylsulfonium hexafluoroantimonate produced an acid. The device still didnot change color. The device changed to pink after 12 hours and redafter 30 hours at room temperature. A similarly prepared unirradiateddevice did not change color under similar conditions after two monthsexposure at room temperature.

EXAMPLE 19 Change in Conductivity

A flexible printed circuit board (EZ Circuit, EZ 1334, Bishop GraphicsInc., Westlake Village, Calif.) having parallel conductive stripes wascoated with 1,6 dichloro-2,4-hexadiyne (referred hereafter to as 1C) tosee experimentally if a conductivity change could be detected under thepredetermined conditions. The resulting device was cooled to -20° C. andexposed to a short wavelength UV lamp for ten minutes for polymerizationof 1C. The device was connected to an electrometer (Kiethley Model 617).The device had an electrical resistance of 1.61×10¹² ohms. The devicewas then activated by applying an adhesive tape (synthetic elastomer(Scotch Grip, 4914, 3M Company) containing pyridine. The decrease inelectrical resistance was determined with time at room temperature. Theresistivity was 3.3×10¹⁰ and 0.8×10⁷ ohms after 2 and 8 hoursrespectively. The device also turned colorless to dark (essentiallybrown-black at the end of the experiment) simultaneously with themeasured changes in the conductivity.

EXAMPLE 20 Bar Coded Device

Bar coding is currently used commercially to track inventory inwarehouses and to read prices of foods in supermarkets. Supermarket'sUniversal Product Code System is different from the industrial barcoding system. The Industrial bar code system can monitor manufacturingprocesses, warehouse inventories, hospital supplies, library books,office records, while the supermarket bar coding is used for both thepurposes, including monitoring inventory and reading package prices atstore check out counters. In most supermarkets in the USA, the prices offoods are read by a bar code reader from the prices printed in form ofbar codes on the containers. In order to demonstrate that the shelf lifemonitoring devices can also be prepared in form of bar codes, two typeof bar coded adhesive tape devices were prepared.

One gram of 4BCMU was dissolved in a mixture of 5 g of chloroform and 4g of acrylic adhesive (Testworth Laboratory) to see experimentally ifthe device could be used as a bar code indicator. The resulting mixturewas coated on a Mylar polyester film using the procedure described inMethod 3. A mask (negative) of a bar code was prepared by copying it ona transparent cellophane film in a copying machine. The mask of the barcode was placed on the 4BCMU coating and exposed to short wavelength UVlight to get the impression of the bar code in blue color (partiallypolymerized 4BCMU). The cellophane mask was then removed. The bar coded4BCMU is the indicator tape. An activator tape comprising of triacetinin the acrylic adhesive was prepared according to the proceduredescribed in Method 5. The device was activated according to theprocedure described in Method 4. The device was placed in an oven at 40°C. After about two hours the blue bars of the device started turning redand at three hours, the bars were red. Though 4BCMU was used todemonstrate the concept, one can print the desired information in theform of bar codes with any of the indicators and activators describedherein and formulated into an appropriate activator tape.

EXAMPLE 21 A Different Method of Creating the Bar Coded Tape Device

An indicator tape consisting of bromophenol blue in a syntheticelastomer (3M #4914) was coated on a Mylar polyester film using anapplicator of cut depth 0.006". Subsequently an applicator of cut depth0.0015% wound around with a nylon thread in a regular pattern was movedacross the above coating creating lines which function as bars andspaces. When this indicator tape was brought in contact with a sodiumcarbonate activator tape, the color of the indicator changed from yellowto green in about 2 hours and then to blue in 12 hours. Thus bar codescan be created by scratching the indicator tape.

The bar code readers can read blue or black colors only. If pp4BCMU isused, the reader would not be able to read the code (the shelf life) andsend a programmed signal to reject the product. In case of bromophenolblue, the reader can be programmed to reject the product if it can readthe code. Thus the system can be totally automated. The bar code readerswill read the information on the product and its shelf lifesimultaneously and print on the purchase receipt. As most majorsupermarkets are equipped with bar code readers, no additional equipmentwill be required.

A barrier matrix layer can also be utilized in the bar code device tointroduce an induction period and also to alter the Eact of thecolor-indicating system.

What is claimed is:
 1. A device for measuring the shelf life of aperishable product having a measurable activativation energy of productdeterioration comprising:a) an indicator tape comprised of a transparentpolymer film and affixed thereto at least one matrix layer containing anindicator composition: b) an activator tape comprised of a substrate andaffixed thereto at least one matrix layer containing an activatorcomposition: c) a composite matrix, comprised of said indicator tape andactivator tape matrix layers, bonded together by at least onewater-impermeable pressure sensitive adhesive, said activatorcomposition being capable of diffusing through said composite matrix ina predetermined time to contact and chemically react with said indicatorcomposition producing a visually observable color change in saidindicator composition, said device being substantially impermeable tomoisture, and said device possessing an activation energy and rateconstant for color change which are substantially the same as theactivation energy and rate constant for product deterioration of theperishable product in the temperature region of monitoring.
 2. Thedevice of claim 1 wherein said composite matrix further comprises atleast one barrier matrix layer permeable to said activator composition,laminated to said activator and indicator matrix layers.
 3. The deviceof claim 1 wherein said polymer film is comprised of polyethylene,polypropylene, polyester, polyurethane, polyamide, polyvinylchloride,polycarbonate or cellulose acetate.
 4. The device of claim 1 whereinsaid substrate is a translucent or opaque polymer film or metal foil. 5.The device of claim 1 wherein said indicator, activator or barriermatrix is independently a resin of the type: epoxy, phenol-formaldehyde,amino-formaldehyde, polyamide, vinyl, acrylic, polyurethane, polyester,alkyd, synthetic elastomer rosin, or pressure sensitive adhesive.
 6. Thedevice of claim 1 wherein said activator is an oxidizing agent and saidindicator is redox dye.
 7. The device of claim 1 wherein said activatoris a reducing agent and said indicator is a redox dye.
 8. The device ofclaim 1 wherein said activator is a base and said indicator is a basesensitive pH dye.
 9. The device of claim 1 wherein said activator is anacid and said indicator is an acid sensitive pH dye.
 10. The device ofclaim 9 where in said activator is citric acid and said indicator dye is2,2',4,4',4"-pentamethoxy triphenylmethanol.
 11. The device of claim 1wherein:a.) the indicator tape comprises: a polyester film, a syntheticelastomer matrix containing 2,2',4,4',4"-pentamethoxy triphenylmethanol;b.) the activator tape comprises: a polyester film, the same syntheticelastomer as in (a) and containing and citric acid in solid solution.12. The device of claim 1 wherein said indicator composition isdisplayed as at least one alphanumeric figure.
 13. The device of claim 1wherein said indicator composition is displayed as at least one barcode.
 14. A process for monitoring the time-temperature storage historyof a perishable product comprising the step of affixing to said productthe device according to claim 1, and activating the device.
 15. Theprocess of claim 14 wherein the activating is by thermal annealing. 16.The process of claim 14 wherein the activating is by radiation.
 17. Theprocess of claim 14 wherein the activating is by applying pressure. 18.A perishable product having the device of claim 1, in activated form,attached thereto.